Hydroxyl-Terminated Thiocarbonate Containing Compounds, Polymers, and Copolymers, and Polyurethanes and Urethane Acrylics Made Therefrom

ABSTRACT

Thiocarbonate compounds are reacted with various polyols to introduce hydroxyl end groups thereto which can be subsequently reacted with urethane forming compounds to form various polyurethanes including block copolymers thereof.

FIELD OF THE INVENTION

Hydroxyl-terminated thiocarbonate containing compounds (HTT) areutilized to form polymers and copolymers useful for numerousapplications. HTT are utilized to form hydroxyl terminated polymers orcopolymers which are used in one embodiment to form thermoplasticpolyurethane in bulk. Waterborne polyurethane dispersions are alsoformed utilizing HTT. In yet another embodiment, solvent basedpolyurethanes are described. The bulk, dispersion, and solvent basedurethanes can contain acrylic repeat units. Various methods are alsodescribed for preparing the various thiocarbonate containing polymersand copolymers of the present invention.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 6,596,899 issued Jul. 22, 2003 relates to as,s′-bis-α,α′-disubstituted-α″-acetic acid)-trithiocarbonate andderivatives thereof can be used as an initiator, chain transfer agent,or terminator for polymerization of monomers such as free radicalpolymerizable monomers. Homopolymers, copolymers, and the like as wellas block copolymers can be made utilizing the trithio carbonate compoundsuch as in a living free radical polymerization as well as to formtelechelic polymers.

U.S. patent application Ser. No. 10/219,403 filed Aug. 15, 2002 relatesto a toughener comprising a trithiocarbonate polymer having an epoxy endgroup which is utilized with various thermosettable polymers such asepoxy, polyurethane, and the like. A toughened composition is made bycuring the thermosettable polymer and the toughener utilizing variouscuring agents. U.S. application Ser. No. 10/219,403 is hereby fullyincorporated by reference.

U.S. patent application Ser. No. 10/278,335 filed Oct. 23, 2002 and Ser.No. 10/681,679 filed Oct. 8, 2003 relate to dithiocarbonate derivatives,along with a process for preparing the same. The dithiocarbonatecompounds can be utilized as initiators, chain transfer agents and/orterminators in controlled free radical polymerizations. Thedithiocarbonates can also be used to produce polymers having a narrowmolecular weight distribution. These compounds can also introducefunctional groups into the resulting polymers. The dithiocarbonatecompounds have low odor and are substantially colorless. U.S.application Ser. Nos. 10/278,335 and 10/681,679 are hereby fullyincorporated by reference.

Telechelic di-functional hydroxyl-terminated vinyl polymers aregenerally not readily available, especially hydroxyl-terminated acrylatepolymers.

SUMMARY OF THE INVENTION

In one embodiment, carboxylate-terminated di- or trithiocarbonates arereacted with a polyfunctional alcohol such as a diol or other polyol toform hydroxyl terminated di- or trithiocarbonates. In a furtherembodiment, one or more monomers, which are the same or different, arereacted into the backbone of the thiocarbonate compound either before orafter reaction with the polyol.

The hydroxyl terminated thiocarbonate containing polymers or copolymersare reacted through the hydroxyl groups along with optional isocyanatereactive compounds, with a mono or desirably a polyisocyanate compoundto form a thermoplastic or thermoset polyurethane. The urethane can beprepared in bulk, solvent or be an aqueous dispersion and optionallycontain an acrylic copolymer.

DETAILED DESCRIPTION OF THE INVENTION

Thiocarbonate Compounds

The thiocarbonate compounds utilized in the present invention arepreferably polythiocarbonates such as dithiocarbonate ortrithiocarbonate compounds and derivatives thereof. By the term“thiocarbonate” it is meant a compound having at least one segmenthaving the formula

where “x” comprises OR, SR, or NR, with R being various hydrocarbon,hetero atom and/or hydrogen containing structures or the like asillustrated hereinbelow, but not limited thereto.

Suitable trithiocarbonate compounds for use in the present invention,but not limited thereto, are disclosed in U.S. Pat. No. 6,596,899 toLai, and U.S. patent application Ser. No. 10/219,403, filed Aug. 15,2002, both hereby fully incorporated by reference including thepreparation thereof. In one embodiment, trithiocarbonate compounds havethe following general formula:

wherein R¹ and R², independently, is the same or different, and is alinear or branched alkyl having from 1 to about 6 carbon atoms, or a C₁to about C₆ alkyl having one or more substituents, or one or more arylsor a substituted aryl group having 1 to 5 substituents on the aryl ring,where the one or more substituents, independently, comprise an alkylhaving from 1 to 6 carbon atoms; or an aryl; or a halogen such asfluorine or chlorine; or a cyano group; or an ether having a total offrom 2 to about 20 carbon atoms such as methoxy, or hexanoxy; or anitro; or combinations thereof. Examples of such compounds includes,s′-bis-2-methyl-2-propanoic acid-trithiocarbonate ands,s′-bis-(2-phenyl-2-propanoic acid)-trithio-carbonate. R¹ and R² canalso form or be a part of a cyclic ring having from 5 to about 12 totalcarbon atoms. R¹ and R² are preferably, independently, methyl or phenylgroups.

The abbreviated reaction formula for one method for the preparation ofs,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonates isgenerally written as follows:

where “x” is halogen and R¹ and R² are the same as set forth above.

The process utilized to form s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds is generally a multi-step process andincludes combining the carbon disulfide and a base whereby anintermediate trithio structure is formed. Ketone can serve as solventfor the carbon disulfide/base reaction and thus can be added in thefirst step of the reaction. In the second step of the reaction, thehaloform, or haloform and ketone, or a α-trihalomethyl-α-alkanol areadded to the trithio intermediate mixture and reacted in the presence ofadditional base. The formed reaction product, is subsequently acidified,thus completing the reaction and forming the above describeds,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compound.

Another aspect of present invention utilizes trithiocarbonate compoundshaving the following formula:

wherein R³ comprises a benzyl group, C₁-C₁₈ alkyl, or substituted alkylsuch as halogen, hydroxyl, or alkoxy, C₁-C₁₈ hydroxyalkyl, aralkyl,cyanoalkyl, aminoalkyl, carboxylalkyl, carboalkoxyalkyl ormercaptoalkyl, and R¹ and R² are defined hereinabove. The resultingcompound is an s-substituted-s′-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate.

Dithiocarbonate compounds which are utilized in some embodiments of thepresent invention are disclosed in U.S. application Ser. No. 10/278,335filed Oct. 23, 2002 and U.S. application Ser. No. 10/681,679 filed Oct.8, 2003, herein fully incorporated by reference including thepreparation thereof. In one embodiment the dithiocarbamate compoundshave the following formula:

wherein j is 1 or 2, with the proviso that when j is 1, T is —(NR⁶R⁷);and when j is 2, T is a divalent radical having a nitrogen atom directlyconnected to each carbon atom of the two thiocarbonyl groups present;wherein R⁴ and R⁵, independently, is the same or different, isoptionally substituted, and is a linear or branched alkyl having from 1to about 6 or about 12 carbon atoms; or an aryl group having from 6 toabout 18 carbon atoms, optionally containing heteroatoms;wherein the R⁴ and/or R⁵ substituents, independently, comprise an alkylhaving from 1 to 6 carbon atoms; an aryl group; a halogen; a cyanogroup; an ether having a total of from 2 to about 20 carbon atoms; anitro; or combinations thereof. R⁴ and R⁵ can also form or be a part ofa substituted or unsubstituted cyclic ring having from 3 to about 12total carbon atoms wherein the substituents are described above. R⁴ andR⁵ are preferably, independently, methyl or phenyl groups;wherein R⁶ and R⁷, independently, is the same or different, optionallyis substituted, optionally contains heteroatoms; and is hydrogen; alinear or branched alkyl having from 1 to about 18 carbon atoms, an arylgroup having from about 6 to about 18 carbon atoms optionally saturatedor unsaturated; an arylalkyl having from about 7 to about 18 carbonatoms; an alkenealkyl having from 3 to about 18 carbon atoms; or derivedfrom a polyalkylene glycol ether having from 3 to about 200 carbonatoms. R⁶ and R⁷ can also be derived from amines such as, but notlimited to, piperazine, morpholine, pyrrolidine, piperidine, 4-alkylamino-2,2,6,6-tetramethyl piperidine,1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine,phenothiazine, iminodibenzyl, phenoxazine,N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine and derivativesthereof. R⁶ and R⁷ can also form a substituted or unsubstituted cyclicring, optionally containing heteroatoms, along with the nitrogen havinga total of from 4 to about 12 carbon atoms, such as benzotriazole,tolyltriazole, imidazole, 2-oxazolidone, 4,4-dimethyloxazolidone and thelike. The R⁶ and R⁷ substituents, independently, can be the same asdescribed herein with respect to R¹³ as set forth herein below. R⁶ andR⁷ are preferably, independently, a phenyl group or an alkyl orsubstituted alkyl having from 1 to about 18 carbon atoms such as amethyl group, or R⁶ and R⁷, independently, are hexamethylene.

In Formula C, when j is 2, the dithiocarbamate compound is abis-S-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate having thefollowing formula:

wherein R⁴ and R⁵ are defined hereinabove; andwherein T is a divalent bridging radical having a nitrogen atom directlyconnected to each of the thiocarbonyl groups present.

When j is 1, T of above formula is (NR⁶R⁷)— and the dithiocarbamatecompound is a S-(α,α′-disubstituted-α″-acetic acid) dithiocarbamategenerally having the following formula:

wherein R⁴, R⁵, R^(6′), and R⁷ are as defined hereinabove.

When j is 2, T is:

wherein R⁸ and R⁹, independently, is the same or different, isoptionally substituted, and is hydrogen, a linear or branched alkylhaving from 1 to about 18 carbon atoms, an aryl group having from about6 to about 18 carbon atoms, an arylalkyl having from 7 to about 18carbon atoms, an alkenealkyl having from 3 to about 18 carbon atoms,wherein the substitutents can be the same as described herein for R¹ andR²;wherein R¹⁰ is optionally substituted, and is an alkylene group havingfrom 1 to about 18 carbon atoms with about 1 to about 6 carbon atomspreferred, or derived from a polyalkylene glycol ether having from 3 toabout 200 carbon atoms, wherein the substituents can be the same asdescribed herein for R¹ and R² or are heteroatoms such as oxygen,nitrogen, sulfur or phosphorous; p is 0 or 1; andwherein R¹¹ and R¹² independently, is the same or different, and isoptionally substituted as described for R¹ and R², and is an alkylenegroup having from 1 to about 4 carbon atoms, with R¹¹ and R¹² preferablyhaving a collective total of 3 to 5 carbon atoms.

In further embodiments, T is:

wherein n is 0 to about 18, with 0 to about 6 preferred;

wherein n is 0 to about 18, with 0 to about 6 preferred;

Some specific non-limiting examples of T bridging radicals are:

wherein n plus m=3 to 5;

The S-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamates are generally areaction product of a metal salt of a dithiocarbamate (can be generatedin situ from amine, carbon disulfide and metal hydroxide), a haloform,and a ketone. A phase transfer catalyst, solvent, and a base such assodium hydroxide or potassium hydroxide can also be utilized to form theS-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamates.

It is to be understood throughout the application formulas, reactionschemes, mechanisms, etc., and the specification that metals such assodium or bases such as sodium hydroxide are referred to and theapplication of the present invention is not meant to be solely limitedthereto. Other metals or bases such as, but not limited to, potassiumand potassium hydroxide, respectively, are contemplated by thedisclosure of the present invention.

Alkoxy dithiocarbonate compounds are utilized in some embodiments of thepresent invention which have the following general formula:

wherein j=1 or 2,

wherein R⁴ and R⁵ are as defined hereinabove;

wherein R¹³ is optionally substituted, and can be a linear or branchedalkyl or alkylene having from 1 to about 12 carbon atoms; an aryl group,optionally saturated or unsaturated; an arylalkyl having from 7 to about18 carbon atoms; an acyl group; an alkenealkyl having from 3 to about 18carbon atoms; an alkene group; an alkylene group; an alkoxyalkyl;derived from a polyalkylene glycol; derived from a polyalkylene glycolmonoalkyl ether having from 3 to 200 carbon atoms; derived from apolyalkylene glycol monoaryl ether having from 3 to 200 carbon atoms; apolyfluoroalkyl such as 2-trifluoroethyl; a phosphorous containingalkyl; or a substituted or unsubstituted aryl ring containingheteroatoms. Alkyl and alkylene groups from 1 to 6 carbon atoms arepreferred;

wherein the R¹³ substituents comprise an alkyl having from 1 to 6 carbonatoms; an aryl; a halogen such as fluorine or chlorine; a cyano group;an amino group; an alkene group; an alkoxycarbonyl group; anaryloxycarbonyl group; a carboxy group; an acyloxy group; a carbamoylgroup; an alkylcarbonyl group; an alkylarylcarbonyl group; anarylcarbonyl group; an arylalkylcarbonyl group; a phthalimido group; amaleimido group; a succinimido group; amidino group; guanidimo group;allyl group; epoxy group; alkoxy group; an alkali metal salt; a cationicsubstitutent such as a quaternary ammonium salt; a hydroxyl group; anether having a total of from 2 to about 20 carbon atoms such as methoxy,or hexanoxy; a nitro; sulfur; phosphorous; a carboalkoxy group; aheterocyclic group containing one or more sulfur, oxygen or nitrogenatoms, or combinations thereof; and wherein “a” is 1 to about 4 with 1or 2 preferred.

The compounds of the above formula are generally identified asO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthates. TheO-alkyl-S-α,α′-disubstituted-α″-acetic acid) xanthates are generated asthe reaction product of an alkoxylate salt, carbon disulfide, ahaloform, and a ketone. Alternatively, a metal salt of xanthate can beutilized in place of the alkoxylate salt and carbon disulfide.

The general reaction mechanism for forming theO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthates is as follows:

It is to be understood that while a few specific thiocarbonate compoundshave been described herein, the present invention is not limited to suchcompounds.

The various thiocarbonate compounds including the varioustrithiocarbonates and the various dithiocarbonates are prepared in amanner as set forth in the above noted U.S. Pat. No. 6,596,899 grantedJul. 22, 2003; U.S. application Ser. No. 10/219,403 filed Aug. 15, 2002;U.S. application Ser. No. 10/278,335 filed Oct. 23, 2002; and U.S.application Ser. No. 10/681,679 filed Oct. 8, 2003, all of which arehereby fully incorporated by reference with regard to reactionconditions including temperature, type and amount of catalysts, and thelike.

Hydroxyl Terminated Thiocarbonate Compounds, Polymers and Copolymers

The acid group terminated thiocarbonate compounds are reacted with apolyfunctional alcohol such as a diol or other polyol to form varioushydroxyl terminated thiocarbonate compounds. Accordingly, monohydroxylthiocarbonates, and dihydroxyl thiocarbonates or other polyol compoundsare formed.

Suitable polyols which are reacted with the thiocarbonate compounds havethe formula: HO—R¹⁴—(OH)_(n)

wherein, the hydroxyl groups are not attached to the same carbon atom,and wherein n is 1 to 7 and preferably is 1. R¹⁴ can preferably be partof at least one simple or substantially hydrocarbon polyol, or lessdesirably part of at least one complex polyol. R¹⁴ is an alkyl orsubstituted alkyl or alkylene group having 2 to 200 carbon atoms anddesirably from 2 to about 10 carbon atoms. The hydroxyl groups can be atthe terminals of a main chain, or a branched chain, or a cyclic chain.The substituted alkyl or alkylene can contain oxygen, ether, ester,sulfide, halide, cyano and any heterocyclic rings includingcarbohydrates.

The so-called simple or substantially hydrocarbon polyhydroxyl compoundsare highly preferred and have alkyl or alkylene groups with thesubstituted alkyl or alkylene groups containing oxygen or a halide.Specific examples include ethylene glycol, 1,2- and 1,3-propyleneglycols, 1,2-, 1,3-, 1,4-, and 2,3-butylene glycols, hexane diols,neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and other glycols suchas bisphenol-A, cyclohexane diol, cyclohexane dimethanol(1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol,2,2,4-trimethyl-1,3-pentanediol, diethylene glycol, triethylene glycol,tetraethylene glycol, polyethylene glycol, dipropylene glycol,polypropylene glycol, dibutylene glycol, polybutylene glycol, dimeratediol, trimethylol propane, pentaerythritol, hydroxylated bisphenols,halogenated diols, and the like, and mixtures thereof. Highly preferreddiols include ethylene glycol, diethylene glycol, propylene glycol,trimethylolpropane, butylene glycol, hexane diol, and neopentyl glycol.

Examples of complex polyols which are not desired but can be utilizedinclude higher polymeric polyols such as polyester polyols and polyetherpolyols, as well as polyhydroxy polyester amides, hydroxyl-containingpolycaprolactones, hydroxyl-containing acrylic interpolymers,hydroxyl-containing epoxides, polyhydroxy polycarbonates, polyhydroxypolyacetals, polyhydroxy polythioethers, polysiloxane polyols,ethoxylated polysiloxane polyols, polybutadiene polyols and hydrogenatedpolybutadiene polyols, polyacrylate polyols, halogenated polyesters andpolyethers, and the like, and mixtures thereof. The polyester polyols,polyether polyols, polycarbonate polyols, polysiloxane polyols,polyacetals, and ethoxylated polysiloxane polyols are preferred.

The polyester polyols typically are esterification products prepared bythe reaction of organic polycarboxylic acids or their anhydrides with astoichiometric excess of a diol. Examples of suitable polyols for use inthe reaction include poly(glycol adipate)s, poly(ethylene terephthalate)polyols, polycaprolactone polyols, orthophthalic polyols, sulfonated andphosphonated polyols, and the like, and mixtures thereof.

The diols used in making the polyester polyols include alkylene glycolshaving from 2 to about 20 total carbon atoms, e.g., ethylene glycol,1,2- and 1,3-propylene glycols, 1,2-, 1,3-, 1,4-, and 2,3-butyleneglycols, hexane diols, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol,and other glycols such as bisphenol-A, cyclohexane diol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol,2,2,4-trimethyl-1,3-pentanediol, diethylene glycol, triethylene glycol,tetraethylene glycol, polyethylene glycol, dipropylene glycol,polypropylene glycol, dibutylene glycol, polybutylene glycol, dimeratediol, Trimethylol propane, pentaerythritol hydroxylated bisphenols,polyether glycols, halogenated diols, and the like, and mixturesthereof. Highly preferred diols include ethylene glycol, diethyleneglycol, butylene glycol, hexane diol, and neopentyl glycol.

Suitable carboxylic acids used in making the polyester polyols generallyhave from 1 to about 20 total carbon atoms and include dicarboxylicacids and tricarboxylic acids and anhydrides, e.g., maleic acid, maleicanhydride, succinic acid, glutaric acid, glutaric anhydride, adipicacid, suberic acid, pimelic acid, azelaic acid, sebacic acid, chlorendicacid, 1,2,4-butane-tricarboxylic acid, phthalic acid, the isomers ofphthalic acid, phthalic anhydride, fumaric acid, dimeric fatty acidssuch as oleic acid, and the like, and mixtures thereof. Preferredpolycarboxylic acids used in making the polyester polyols includealiphatic or aromatic dibasic acids.

The preferred polyester polyol is a diol. Preferred polyester diolsinclude poly(butanediol adipate); hexane diol adipic acid andisophthalic, acid polyesters such as hexane adipate isophthalatepolyester; hexane diol neopentyl glycol adipic acid polyester diols,e.g., Piothane 67-3000 HNA (Panolam Industries) and Piothane 67-1000HNA; as well as propylene glycol maleic anhydride adipic acid polyesterdiols, e.g., Piothane 50-1000 PMA; and hexane diol neopentyl glycolfumaric acid polyester diols, e.g., Piothane 67-500 HNF. Other preferredpolyester diols include Rucoflex® S1015-35, S1040-35, and S-1040-110(Bayer Corporation

Polyether diols may be substituted in whole or in part for the polyesterdiols. Polyether polyols contain from 2 to about 15 carbon atoms in therepeat unit and are obtained in known manner by the reaction of (A) thestarting compounds that contain reactive hydrogen atoms, such as wateror the diols set forth for preparing the polyester polyols, and (B)alkylene oxides, such as ethylene oxide, propylene oxide, butyleneoxide, styrene oxide, tetrahydrofuran, epichlorohydrin, and the like,and mixtures thereof. Preferred polyethers include poly(propyleneglycol), polytetrahydrofuran, and copolymers of poly(ethylene glycol)and poly(propylene glycol).

Polycarbonates include those obtained from the reaction of (A) diolssuch 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol,triethylene glycol, tetraethylene glycol, and the like, and mixturesthereof with (B) diarylcarbonates such as diphenylcarbonate or phosgene.

Polyacetals include the compounds that can be prepared from the reactionof (A) aldehydes, such as formaldehyde and the like, and (B) glycolssuch as diethylene glycol, triethylene glycol, ethoxylated4,4′-dihydroxy-diphenyldimethylmethane, 1,6-hexanediol, and the like.Polyacetals can also be prepared by the polymerization of cyclicacetals.

Polysiloxanes include polydialkylsiloxane diols wherein the alkyl grouphas from 1 to about 3 carbon atoms such as polydimethylsiloxane diolmade by GE such as OSI-14209, and by GEL-EST such as DMS-C21.

The aforementioned diols useful in making polyester polyols can also beused as additional reactants to prepare the isocyanate terminatedprepolymer.

The hydroxyl terminated thiocarbonate compounds are formed by combiningthe desired thiocarbonate and base diol or polyol in a suitable reactionvessel. The reaction is an esterification and the same is known to theart and to the literature. For example, usually an acid catalyst such asp-toluenesulfonic acid is utilized and a reaction temperature is fromabout 20° C. to about 200° C. and preferably from about 80° C. to about150° C. The number of repeat units derived from the thiocarbonatecompounds in the hydroxyl terminated thiocarbonate compositions rangesgenerally from about 1 to about 20, and desirably from about 1 to about10.

For example, a general reaction mechanism for preparing atrithiocarbonate diol is:

wherein “a” is from about 1 to about 10 or about 20, and desirably fromabout 1 to about 5, and R¹, R² and R¹⁴ are defined herein above. Thenumber of repeat groups “a” will vary depending upon the equivalentratio of hydroxyl groups to carboxylic acid groups. Thus, when theOH/COOH ratio is preferably about 2 or greater, generally about one “a”unit will predominate, and the product can be a mixture of different “a”numbers.

A general reaction mechanism for preparing a trithiocarbonate polyolutilizing the trithiocarbonate of Formula B is as follows.

where R¹, R², R³, and R¹⁴ are defined as hereinabove. In order to form ahydroxyl terminated compound as set forth in Formula BB, the equivalentratio of hydroxyl groups to carboxylic acid end groups, i.e. OH/COOH ispreferably about 2 or greater. If lower equivalent ratios are utilized,non-hydroxyl terminated compounds can exist.

The general reaction for preparing a dithiocarbamate polyol of Formula Cwhere j is 1 is as follows:

where R⁴, R⁵, R¹⁴, and R⁶ and R⁷ are defined herein above. In order toform a hydroxyl terminated compound as set forth in Formula CC, theequivalent ratio of hydroxyl groups to carboxylic acid end groups, i.e.OH/COOH is preferably about 2 or greater. If lower equivalent ratios areutilized, non-hydroxyl terminated compounds can exist.

Reaction of the above dithiocarbamate C compound wherein j is 2 is asfollows:

where R⁴, R⁵, R¹⁴, and T are as defined herein above and “c” is fromabout 1 to about 10 or about 20 and desirably from about 1 to about 5.The number of repeat groups “c” will vary depending upon the equivalentratio of hydroxyl groups to carboxylic acid groups. Thus, when theOH/COOH ratio is preferably about 2 or greater, generally about one “c”unit will predominate, and the product can be a mixture of different “c”numbers.

When the dithiocarbonate is an alkoxy dithiocarbonate of Formula E, jcan be 1 or 2. Where j=1, the general reaction is as follows:

wherein R⁴, R⁵, and R¹³ are defined hereinabove. In order to form ahydroxyl terminated compound as set forth in Formula EE, the equivalentratio of hydroxyl groups to carboxylic acid end groups, i.e. OH/COOH ispreferably about 2 or greater. If lower equivalent ratios are utilized,non-hydroxyl terminated compounds can exist.

When the dithiocarbonate is an alkoxy dithiocarbonate of Formula Ewherein j=2, the general reaction is as follows

where R⁴, R⁵, and R¹³, are defined herein above and “e” is from about 1to about 10 or about 20, and desirably from 1 to about 5. The number ofrepeat groups “e” will vary depending upon the equivalent ratio ofhydroxyl groups to carboxylic acid groups. Thus, when the OH—COOH ratiois preferably about 2 or greater, generally about one “e” unit willpredominate, and the product can be a mixture of different “e” numbers.

In a similar manner, the reaction of other thiocarbonate compounds andother polyols will form hydroxyl terminated thiocarbonate polymers.

Monomer Incorporation

In a further embodiment, the thiocarbonate compounds and/or the hydroxylterminated thiocarbonate compounds are reacted with one or more, same ordifferent monomers through a reversible polymerization process, such asa reversible addition—fragmentation transfer (RAFT) polymerization,thereby incorporating the monomer(s) into the backbone of thethiocarbonate compound thus forming a thiocarbonate polymer orcopolymer. Although the one or more monomers can first be reacted intothe thiocarbonate compounds, it is preferred that the thiocarbonatecompounds are reacted to contain hydroxyl end groups before the one ormore monomers are reacted into the backbone of the thiocarbonate.

The monomers include one or more conjugated diene monomers or one ormore vinyl containing monomers, or combinations thereof. The various oneor more free radically polymerizable monomer as well as the variousreaction conditions thereof including types of initiators, catalysts,solvents, and the like are set forth in U.S. Pat. No. 6,596,889 grantedJul. 22, 2003; U.S. application Ser. No. 10/219,403 filed Aug. 15, 2002;U.S. application Ser. No. 10/278,335 filed Oct. 23, 2002; and U.S.application Ser. No. 10/681,679 filed Oct. 8, 2003, all of which arehereby fully incorporated by reference with regard to all aspectsthereof.

The diene monomers have a total of from 4 to about 12 carbon atoms andexamples include, but are not limited to, 1,3-butadine, isoprene,1,3-pentadiene, 2,3-dimethyl-1-3-butadeine, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene, and combinations thereof.

The vinyl containing monomers have the following structure:

where R¹⁵ comprises hydrogen, halogen, C₁ to C₄ alkyl, or substitutedC₁-C₄ alkyl wherein the substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR¹⁷), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc or the like or an ammoniumsalt, acyloxy, aroyloxy(O₂CR¹⁷), alkoxy-carbonyl(CO₂R¹⁷), oraryloxy-carbonyl; and R¹⁶ comprises hydrogen, R¹⁷, CO₂H, CO₂R¹⁷, COR¹⁷,CN, CONH₂, CONHR¹⁷, O₂CR¹⁷, OR¹⁷, or halogen. R¹⁷, independently,comprises C₁-C₁₈ alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl,heterocyclyl, aralkyl, or alkaryl, wherein the substituentsindependently comprise one or more epoxy, hydroxy, alkoxy, acyl,acyloxy, carboxy (and salts), sulfonic acid (and salts), alkoxy- oraryloxy-carbonyl, dicyanato, cyano, silyl, halo and dialkylamino.Optionally, the monomers comprise maleic anhydride, N-vinyl pyrrolidone,N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate andcyclo-polymerizable monomers. Monomers CH₂═CR¹⁵R¹⁶ as used hereininclude C₁-C₈ acrylates and methacrylates, acrylate and methacrylateesters, acrylic and methacrylic acid, styrene, a methyl styrene, C₁,-C₁₂alkyl styrenes with substitute groups both either on the chain or on thering, acrylamide, methacrylamide, N- and N,N-alkylacrylamide andmethacrylonitrile, mixtures of these monomers, and mixtures of thesemonomers with other monomers. As one skilled in the art would recognize,the choice of comonomers is determined by their steric and electronicproperties. The factors which determine copolymerizability of variousmonomers are well documented in the art. For example, see: Greenley, R.Z., in Polymer Handbook, 3^(rd) Edition (Brandup, J., and Immergut, E.H. Eds.) Wiley: New York, 1989 p II-53.

Specific monomers or comonomers include the following: methylmethacrylate, ethyl methacrylate, propyl methacrylate (all isomers),butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornylmethacrylate, methacrylic acid, benzyl methacrylate, phenylmethacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate,ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (allisomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid,benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, functionalmethacrylates, acrylates such as glycidyl methacrylate, 2-hydroxyethylmethacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutylmethacrylate (all isomers), N,N-dimethylaminoethyl methacrylate,N,N-diethylaminoethyl methacrylate, and triethyleneglycol methacrylate,itaconic anhydride, itaconic acid; metal salts such as but not limitedto sodium and zinc of all monomeric acids, such as but not limited to,itaconic acid and 2-acrylamido-2-methyl-1-propanesulfonic acid, or thelike; N-vinylimidazole, vinylpyridine N-oxide, 4-vinylpyridinecarboxymethylbetaine, diallyl dimethylammonium chloride,p-styrenesulfonic acid, p-styrenecarboxylic acid, 2-dimethylaminioethylacrylate and its alkyl/hydrogen halide salts, 2-dimethyl-aminoethylmethacrylate and its alkyl/hydrogen halide salts,N-(3-dimethyl-aminopropyl)acrylamide,N-(3-dimethylaminoproyl)methacrylamide, diacetone acrylamide,2-(acetoacetoxy)ethyl methacrylate, 2-(acryloyloxy)ethyl acetoacetate,3-trialkoxysilyipropylmethacrylate (methoxy, ethoxy, isopropoxy, etc),glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (allisomers), hydroxybutyl acrylate (all isomers), N,N-diethylaminoethylacrylate, triethyleneglycol acrylate, methacrylamide,N-methylacrylamide, N,N-dimethyl-acrylamide, N-tertbutylmethacrylamide,N—N-butylmethacrylamide, N-methylol-methacrylamide,N-ethylolmethacrylamide, N-tertbutylacrylamide, N—N-butyl-acrylamide,N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (allisomers), diethylaminostyrene (all isomers), alpha-methylvinyl benzoicacid (all isomers), diethylamino alpha-methylstyrene (all isomers),p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic sodium salt,trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate,tributoxysilyipropyl methacrylate, dimethoxy-methylsilylpropylmethacrylate, diethoxymethylsilylpropyl methacrylate,dibutoxy-methylsilylpropyl methacrylate, diisopropoxymethylsilylpropylmethacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropylmethacrylate, dibutoxy silylpropyl methacrylate, diisopropoxysilylpropylmethacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropylacrylate, tributoxysilylpropyl acrylate, dimethoxy-methylsilylpropylacrylate, diethoxymethylsilylpropyl acrylate, dibutoxy-methylsilylpropylacrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxy-silylpropylacrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate,diisopropoxysilylpropyl amiate, vinyl acetate, vinyl butyrate, vinylbenzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleicanhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone,N-vinylcarbazole, butadiene, isoprene, chloroprene, ethylene, andpropylene, and combinations thereof.

Preferred monomers are C₁-C₁₈ acrylates; acrylic acid; C₁-C₈ monoalkyland dialkyl acrylamides; a combination of C₁-C₈ acrylates andmethacrylates; a combination of said acrylamides and C₁-C₈ monoalkyl anddialkyl methacrylamides; styrene; butadiene; isoprene and acrylonitrile.

In order to initiate the free radical polymerization process, it isoften desirable to utilize an initiator as a source for initiating freeradicals. Generally, the source of initiating radicals can be anysuitable method of generating free radicals such as the thermallyinduced homolytic scission of a suitable compound(s) (thermal initiatorssuch as peroxides, peroxyesters, or azo compounds), the spontaneousgeneration from monomer (e.g., styrene), redox initiating systems,photochemical initiating systems or high energy radiation such aselectron beam, X- or gamma-radiation. The initiating system is chosensuch that under the reaction conditions there is no substantial adverseinteraction of the initiator or the initiating radicals with thetransfer agent under the conditions of the experiment. The initiatorshould also have the requisite solubility in the reaction medium ormonomer mixture. The thiocarbonate compounds of the invention can serveas an initiator, but the reaction must be run at a higher temperature.Therefore, optionally it is desirable to utilize an initiator other thanthe thiocarbonates compounds of the present invention.

Thermal initiators are chosen to have an appropriate half-life at thetemperature of polymerization. These initiators can include one or moreof the following compounds:

-   2,2′-azobis(isobutyronitrile) (AIBN), 2,2′-azobis(2-cyano-2-butane),    dimethyl-   2,2′-azobisdimethylisobutyrate, 4,4′-azobis(4-cyanopentanoic acid),-   1,1′-azobis(cyclohexanecarbanitrile), 2-(t-butylazo)-2-cyanopropane,-   2,2′-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)-2-hydroxyethyl]propionamide,-   2,2′-azobis[2-methyl-N-hydroxyethyl)]-propionamide,    2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride,    2,2′-azobis(2-amidinopropane) dihydrochloride,    2,2′-azobis(N,N′-dimethyleneisobutyramine),    2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide),-   2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide),-   2,2′-azobis[2-methyl-N-(2-hydroxyethyl) propionamide],-   2,2′-azobis(isobutyramide) dehydrate,    2,2′-azobis(2,2,4-trimethylpentane),-   2,2′-azobis(2-methylpropane), t-butyl peroxyacetate, t-butyl    peroxybenzoate, t-butyl peroxyoctoate, t-butylperoxy-neodecanoate,    t-butylperoxy isobutyrate, t-amyl peroxypivalate, t-butyl    peroxypivalate, di-isopropyl peroxydicarbonate, dicyclohexyl    peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide,    dilauroylperoxide, potassium peroxy-disulfate, ammonium    peroxydisulfate, di-t-butyl hyponitrite, dicumyl hyponitrite.

Photochemical initiator systems are chosen to have the requisitesolubility in the reaction medium or monomer mixture and have anappropriate quantum yield for radical production under the conditions ofthe polymerization. Examples include benzoin derivatives, benzophenone,acyl phosphine oxides, and photo-redox systems production under theconditions of the polymerization; these initiating systems can includecombinations of the following oxidants and reductants:

-   -   oxidants: potassium peroxydisulfate, hydrogen peroxide, t-butyl        hydroperoxide reductants: iron (11), titanium (111), potassium        thiosulfite, potassium bisulfite.

Other suitable initiating systems are described in recent texts. See,for example, Moad and Solomon “The Chemistry of Free RadicalPolymerization”. Pergamon, London. 1995. pp 53-95.

The preferred initiators of the present invention are2,2′-azobis(isobutyronitrile)(AIBN), or 4,4′-azobis(4-cyanopentanoicacid), or 2,2′-azobis(2-cyano-2-butane), or1,1′-azobis(cyclohexanecarbanitrile). The amount of initiators utilizedin the polymerization process can vary widely as generally from about0.001 percent to about 99 percent, and desirably from about 0.01 percentto about 50 or 75 percent based on the total moles of chain transferagent utilized. Preferably small amounts are utilized from about 0.1percent to about 5, 10, 15, 20, or 25 mole percent based on the totalmoles of chain transfer agent utilized, i.e. saids,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatescompounds. In order to form polymers which are predominately telechelic,initiators other than the above thiocarbonate compounds are utilized inlesser amounts, such as from about 0.001 percent to about 5 percent,desirably from about 0.01 percent to about 4.5 percent, and preferablyfrom about 0.1 percent to about 3 percent based on the molar equivalentto the total moles of chain transfer agent utilized.

Optionally, as noted above, solvents can be utilized in the free radicalpolymerization process. Examples of such solvents include, but are notlimited to, C₆-C₁₂ alkanes, ethyl acetate, toluene, chlorobenzene,acetone, t-butyl alcohol, n-methylpyrrolidone, dimethylformamide, andsuper critical CO₂. The solvents are chosen so that they do notsubstantially chain transfer themselves. The amount of solvent utilizedin the present invention polymerization process is generally from about10 percent to about 500 percent the weight of the monomer, andpreferably from about 50 percent to about 200 percent the weight of themonomer utilized in the polymerization.

The one or more conjugated diene and/or vinyl monomers can beincorporated into the backbone of the thiocarbonate compound before itis reacted with a polyol and the same reaction scheme is set forth inU.S. Pat. No. 6,596,899 granted Jul. 22, 2003, or in U.S. patentapplication Ser. No. 10/278,335 filed Oct. 23, 2002, or in U.S. patentapplication Ser. No. 10/681,679 filed Oct. 8, 2003 which are herebyfully incorporated by reference.

Alternatively, desirably, and in a similar manner, the various one ormore conjugated diene monomers and/or the one or more vinyl monomers areincorporated into the backbone of the hydroxyl-terminated thiocarbonatecompound.

With respect to the hydroxyl terminated thiocarbonate of Formula AA, thegeneral reaction scheme for reacting one or more conjugated dienemonomers and/or one or more vinyl monomers into the backbone of thehydroxyl-terminated trithiocarbonate compound is as follows:

wherein R¹, R², R¹⁴, R¹⁵, and R¹⁶ are defined hereinabove, “a” is as setforth hereinabove, and m, m′, n and n′, independently, is generally fromabout 1 to about 10,000, desirably from about 2 to about 500, andpreferably from about 5 to about 100. Naturally, any remaining monomeris removed.

With respect to the hydroxyl-terminated trithiocarbonate compound ofFormula BB, the general reaction scheme is as follows:

wherein R¹, R², R³, R¹⁴, R¹⁵, and R¹⁶ are defined hereinabove, and m andm′, independently, is generally from about 1 to about 10,000, desirablyfrom about 2 to about 500, and preferably from about 5 to about 100.Naturally, any remaining monomer is removed.

With regard to the hydroxyl-terminated trithiocarbonate compound ofFormula CC where j is 1, the general reaction scheme is as follows:

wherein R⁴, R⁵, R⁶, R⁷, R¹⁴, R¹⁵, and R¹⁶ are defined hereinabove, and mand m′ is generally from about 1 to about 10,000, desirably from about 2to about 500, and preferably from about 5 to about 100. Naturally, anyremaining monomer is removed.

With respect to the high temperature dithiocarbonate compound of FormulaCC where j is 2, the general reaction scheme is as follows.

wherein R⁴, R⁵, R¹⁴, R¹⁵, R¹⁶, and T are defined hereinabove, wherein cis from about 1 to about 10 or about 20, and preferably from 1 to about5, and wherein m, m′, n, and n′, independently, are generally from about1 to about 10,000, desirably from about 2 to about 500, and preferablyfrom about 5 to about 100. Naturally, any remaining monomer is removed.

With respect to the high temperature dithiocarbonate of Formula EE, thegeneral reaction scheme is as follows:

wherein R⁴, R⁵, R¹³, R¹⁴, R¹⁵, and R¹⁶, are defined hereinabove, whereinm and m′ is generally from about 1 to about 10,000, desirably from about2 to about 500, and preferably from about 5 to about 100. Naturally anyremaining monomer is removed.

With respect to the hydroxyl-terminated dithiocarbonate of Formula EEwhere j is 2, the general reaction scheme is as follows:

wherein R⁴, R⁵, R¹³, R¹⁴, R¹⁵, and R¹⁶, are defined hereinabove, whereine is from about 1 to about 10 or about 20, and preferably from about 1to about 5, and wherein m, m′, n, and n′, independently, is from about 1to about 10,000, desirably from about 2 to about 500, and preferablyfrom about 5 to about 100. Naturally any remaining monomer is removed.

Reactions of other thiocarbonates with various conjugated diene and/orvinyl monomers react in a similar manner, and reaction mechanisms areset forth in more detail in U.S. Pat. No. 6,596,899 issued Jul. 22,2003; U.S. patent application Ser. Nos. 10/219,403 filed Aug. 15, 2002;10/278,335 filed Oct. 23, 2002; and 10/681,679 filed Oct. 8, 2003 whichare hereby fully incorporated by reference.

The resulting polymers or copolymers are either telechelic polymers withhydroxyl functional groups at both ends of the chain, or a polymerhaving a single hydroxyl functional end group and also a small amount ofan initiator terminated chain (formed by using a conventional initiatorsuch as AIBN). As stated above, the ratios between the resultingpolymers can be controlled to give desired results and generally dependon the amount of initiator utilized. The greater the amount of the otherinitiator utilized proportionally decreases the amount of telechelicpolymers formed. Generally, the number of the repeat groups of the oneor more monomers per polymer chain such as m, m′, n or n′ have a widerange as set forth above. Inasmuch as one or more vinyl monomers and/orone or more diene monomers can be utilized, it is to be understood thatrepeat groups of the hydroxyl terminated thiocarbonate polymers orcopolymers of the present invention can be the same or different. Thatis, random copolymers, terpolymers, etc., can be formed within the oneor more m, m′, n, or n′ blocks as noted, as well as block copolymers canbe formed by initially adding one monomer and then subsequently adding adifferent monomer (e.g. an internal block copolymer).

The invention has wide applicability in the field of free radicalpolymerization and can be used to produce polymers and compositions forcoatings, a wide variety of which can be applied to numerous differentsubstrates. Such coatings can further include pigments, durabilityagents, corrosion and oxidation inhibitors, rheology control agents,metallic flakes and other additives. Block and star, and branchedpolymers can be used as compatibilizers, thermoplastic elastomers,dispersing agents or rheology control agents. Additional applicationsfor polymers of the invention are in the fields of imaging, electronics(e.g., photoresists), engineering plastics, adhesives, sealants, andpolymers in general.

The reaction conditions are chosen as known to one skilled in the art sothat the temperature utilized will generate a radical in a controlledfashion, wherein the temperature is generally from about roomtemperature to about 200° C. The reaction can be run at temperatureslower than room temperature, but it is impractical to do so. Thetemperature often depends on the initiator chosen for the reaction, forexample, when AIBN is utilized, the temperature generally is from about40° C. to about 80° C., when 4,4′-azobis(4-cyanovaleric) acid isutilized, the temperature generally is from about 50° C. to about 90°C., when di-t-butylperoxide is utilized, the temperature generally isfrom about 110° C. to about 160° C., when a thiocarbonate is utilized,the temperature is generally from about 80° C. to about 200° C.

EXAMPLE 1 Synthesis of the Monohydroxyl Terminated DithiocarbamateCompound

Procedure:

In a 1000 ml jacketed reaction vessel equipped with a mechanicalstirrer, a thermometer, a reflux condenser, distillation adaptor, and anaddition funnel, 500 grams of ethylene glycol was added and heated to90° C. under nitrogen. A mixture of 200 grams of the dithiocarbonate and18.37 grams of the p-toluenesulfonic acid monohydrate was added throughthe addition funnel dropwise to maintain reaction temperature. A mixtureof dithiocarbonate and p-toluenesulfonic acid was added, heated to 110°C. and 60 mm Hg of partial vacuum was pulled to collect water. When nomore water was collected and the head temperature dropped and levelsdropped off, the vacuum was slowly increased to full vacuum to distilloff excess ethylene glycol. When reaction temperature exceeded 90° C.,the reaction was stopped. For purification, 250 ml toluene was addedwhen the reaction had cooled and stirred to room temperature. Themixture was then transferred to a separatory funnel and extracted threetimes with 100 ml saturated sodium carbonate. The aqueous fractions werediscarded and the organic (toluene) fraction collected. 10 grams ofmagnesium sulfate was added. After one hour, the filter contents wereconcentrated with a rotavaporator at 80° C., full vacuum, for an hour.An orange, viscous product was collected and the structure confirmedwith mass spectrometry, nuclear magnetic resonance and hydroxyl number.

EXAMPLE 2 Synthesis of Dihydroxyl Dithiocarbamate Compound

Procedure:

In a 500 ml jacketed reaction vessel equipped with a mechanical stirrer,a thermometer, a reflex condenser, distillation adaptor, and an additionfunnel, 150 grams of ethylene glycol and 5.57 grams of thep-toluenesulfonic acid monohydrate was added and heated to 110° C. undernitrogen. A mixture of 60 grams of the dithiocarbonate was added throughthe addition funnel dropwise to maintain reaction temperature. Onceadded, the partial vacuum was increased to 60 mmHg to remove water. Whenlittle water was coming off and head temperature dropped and levelsdropped off, the temperature was increased to 120° C. to remove morewater. When no more water was removed and head temperature dropped andstabilized, the vacuum was increased to full vacuum to remove excessethylene glycol. When temperature exceeded 110° C., the heat was turnedoff. When reaction was room temperature, added 65 ml methyl isobutylketone and stirred till homogenous. Added 33 ml of 5% sodium hydroxide,stirred and transferred to a separatory funnel. Collected organic(methyl isobutyl ketone) fraction. Extracted aqueous layer two timeseach with 16 ml methyl isobutyl ketone. Added these two methyl isobutylketone fractions to the previous organic fraction. The organic fractionwas stirred at room temperature until a white precipitate dropped outand became thick. Refrigerated, buchner filtered and collected whitesolid. Confirmed structure by nuclear magnetic resonance, massspectrometry and hydroxyl number.

EXAMPLE 3 Synthesis of Monohydroxyl Dithiocarbamate Polymer ContainingRepeat Units Derived from Ethyl Acrylate

Procedure:

In a 1000 ml reaction vessel equipped with mechanical stirrer,thermometer, reflux condenser and nitrogen purge, 44.2 grams of themonohydroxyl terminated dithiocarbonate, 395.9 grams of ethyl acrylate,400 ml of MEK, and 0.5071 grams of Azo catalyst were added. After anitrogen blanket was applied, the reactants were heated to 65° C. Afterno further exotherm was observed, the reactants were heated to 80° C.for a period of about 5 hours. The solvent was removed by rotavaporationunder full vacuum and 80° C. and a viscous product collected. Thestructure was confirmed by size exclusion chromatography, hydroxylnumber and matrix-assisted laser desorbtion ionization.

EXAMPLE 4 Synthesis of Dihydroxyl Dithiocarbamate Polymer ContainingRepeat Units Derived from Butyl Acrylate

Procedure:

In a 2000 ml reaction vessel equipped with mechanical stirrer,thermometer, reflux condenser and nitrogen purge, 58.0 grams of thedihydroxyl terminated dithiocarbonate, 524.33 grams of butyl acrylate,0.3323 grams of Azo catalyst, and 580 ml of MEK were added. After anitrogen blanket was applied, the reactants were heated to 65° C. for aperiod of about 4.5 hours. Solvent was removed by rotavaporation underfull vacuum and 80° C. The viscous product was collected. Confirmedstructure by size exclusion chromatography, hydroxyl number andmatrix-assisted laser de desorbtion ionization.

EXAMPLE 5 Synthesis of a Dihydroxyl Dithiocarbamate Copolymer ContainingRepeat Units Derived from Ethyl Acrylate and Acrylonitrile

Procedure:

In a 2000 ml reaction vessel equipped with mechanical stirrer,thermometer, reflux condenser and nitrogen purge, 124.5 grams of themonohydroxyl terminated dithiocarbonate, 465 grams of ethyl acrylate, 35grams of acrylonitrile, 0.9611 grams of Azo catalyst, and 625 ml ofdimethylforamide were added. After a nitrogen blanket was applied, thereactants were heated to 65° C. for a period of about 8.5 hours. Solventwas removed by rotavaporation under full vacuum and 80° C. The viscousproduct was collected. Confirmed structure by size exclusionchromatography, hydroxyl number and matrix-assisted laser desorbtionionization.

EXAMPLE 6 Synthesis of a Dihydroxyl Dithiocarbamate Copolymer ContainingRepeat Units Derived from Ethyl Acrylate and Diacetone Acrylamide

Procedure:

In a 2000 ml reaction vessel equipped with mechanical stirrer,thermometer, reflux condenser and nitrogen purge, 139.324 grams of thedihydroxyl terminated dithiocarbonate, 560 grams of ethyl acrylate, 140grams of diacetone acrylamide, 840 ml of MEK, and 0.8073 grams of Azocatalyst were added. After a nitrogen blanket was applied, the reactantswere heated to 65° C. After no further exotherm was observed, thereactants were heated to 80° C. for a period of about 7 hours. Removedsolvent by rotavaporation under full vacuum and 80° C. The viscousproduct was collected. Confirmed structure by size exclusionchromatography, hydroxyl number and matrix-assisted laser desorbtionionization.

EXAMPLE 7 Synthesis of the Mono-Dihydroxyl Terminated DithiocarbamateCompound (from Mono Dithiocarbonate and Trimethylolpropane)

Procedure:

In a 100 ml jacketed reaction vessel equipped with a mechanical stirrer,a thermometer, a reflex condenser, distillation adaptor, and anadditional funnel, 33 grams of trimethylolpropane was added and heatedto 80° C. under nitrogen. A mixture of 10 grams of the dithiocarbonateand 0.87 grams of the p-toluenesulfonic acid monohydrate was addedthrough the addition funnel in aliquots to maintain reactiontemperature. Once the mixture of dithiocarbonate and p-toluenesulfonicacid was added, it was heated to 110° C. and 60 mmHg of partial vacuumto collect water. The reaction was stopped when no more water wascollected and the reaction head temperature had dropped. Forpurification, 50 ml toluene was added and stirred at approximately 70°C., cooled and collected top toluene layer, concentrate. An orange,viscous product was collected and the structure was confirmed with massspectrometry, nuclear magnetic resonance and hydroxyl number.

EXAMPLE 8 Synthesis of Dihydroxyl Dithiocarbamate Compound (1,3Propanediol Derivative)

Procedure:

In a 2000 ml jacketed reaction vessel equipped with a mechanicalstirrer, a thermometer, a reflex condenser, distillation adaptor, and anaddition funnel, 685 grams of 1,3 propanediol and 26.1 grams of thep-toluenesulfonic acid monohydrate was added and heated to 110° C. undernitrogen. Dithiocarbonate was added in four aliquots over one hour. Onceadded, distillation apparatus was attached and the partial vacuum wasincreased to 60 mmHg to remove water. When little water was coming offand the head temperature had dropped and leveled off, the temperaturewas increased to 120° C. to remove more water. When no more water wasremoved and the head temperature had stabilized, the vacuum wasincreased to full to remove excess 1,3 propanediol. When the temperatureexceeded 100° C., the heat was turned off. When reaction reached roomtemperature, 400 ml chloroform was added and stirred till homogenous andthen transferred to a separatory funnel and washed three times with 200ml saturated sodium carbonate solution. The chloroform layer wascollected, 10 g magnesium sulfate was added and let sit for at least anhour. The chloroform fraction was filtered and concentrated. To theconcentrate was added 400 ml toluene and stirred at 80° C. tillhomogenous. Then it was stirred to room temperature. Refrigerated,buchner filter and collected light yellow solid. Confirmed structure bynuclear magnetic resonance, mass spectrometry and hydroxyl number.

EXAMPLE 9 Synthesis of a Dihydroxy Trithiocarbonate Compound of FormulaAA

Procedure:

The reaction was run in a 100 ml, 3 port reaction vessel equipped with amagnetic stirring, mantle, thermowatch, condenser, distillation adaptor,receiver, thermometers, partial vacuum, solid addition funnel, under anitrogen blanket. 50 grams of ethylene glycol was then charged under anitrogen blanket and the solution heated to 80° C. At 80° C., 20 gramsof TTC and 2.7 grams of pTSA were slowly added through addition funnelin aliquots. When the TTC/pTSA was added, the partial vacuum was startedand increased to 60 mmHg. When no more condensate was collected at 110°C., 60 mm Hg, the temperature was set to 90° C. The vacuum was increasedto full to distill off diol. When pot temperature was 90° C. to 95° C.,the heat was turned off and workup. Confirmed structure by nuclearmagnetic resonance, mass spectrometry and hydroxyl number.

EXAMPLE 10

Procedure:

O-ethyl-s-(isobutyric acid) xanthate (100 g), 300 g ofpolytetrahydrofuran, (molecular number equals about 250) andp-toluenesulfonic acid (10 g) were mixed and heated to 110° C. todistill off water that is formed. After five hours, unreactedpolytetrahydrofuran was distilled under 1 mm Hg vacuum. The residue wasdissolved in 500 ml ether, dried over sodium sulfate and concentrated toyield oil. Confirmed structure by nuclear magnetic resonance, massspectrometry and hydroxyl number.

Thermoplastic Polyurethanes (TPU) Made from Hydroxyl-TerminatedThiocarbonate Compounds, Polymers, and Copolymers

Thermoplastic polyurethanes are generally formed in one embodiment ofthe invention by reacting the hydroxyl group terminated thiocarbonatecompounds, polymers, or copolymers, or a combination thereof with anisocyanate group-containing compound optionally in the presence of acatalyst generally followed by chain extension. The thermoplasticurethanes can be made by can be made preferably by a waterborne process,or by a solvent process, or by extrusion. Optionally thermosets can beformed utilizing either crosslinking agents or self-crosslinkingcompounds incorporated within various urethane components. The term“polyurethane composition” when utilized in the specification generallyrefers to a composition containing reagents utilized to form apolyurethane, or a composition subsequent to the reaction of thepolyurethane forming reagents by some process or mechanism. Thethermoplastic polyurethanes of the invention are able to be melted andreshaped by some process such as extrusion or molding, or cast into filmfrom solution and are thus substantially uncrosslinked.

Isocyanates

Suitable isocyanates comprise mono-isocyanates and polyisocyanates suchas di-isocyanates, tri-isocyanates, and functionalized isocyanateshaving a total of from 4 to about 10, or about 15, or about 20 carbonatoms, or mixtures thereof. In one embodiment, suitable isocyanates havean average of one or more, or about two to about four isocyanate groups,preferably an average of about two isocyanate groups and includealiphatic, cycloaliphatic, aromatic including any aliphatic groups, andtrialkoxysilylalkyl isocyanates, used alone or in mixtures of two ormore. Diisocyanates are highly preferred in order to producethermoplastic polyurethanes.

Specific examples of suitable aliphatic polyisocyanates include alpha,omega-alkylene diisocyanates having from 5 to about 20 carbon atoms,such as tetramethylene diisocyanate, hexamethylene-1,6-diisocyanate(HDI), decamethylene diisocyanate, 1,12-dodecane diisocyanate,2,2,4-trimethyl-hexamethylene diisocyanate,2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, and the like. Polyisocyanates having fewer than 5 carbonatoms can be used but are less preferred because of their highvolatility and toxicity. Aromatic aliphatic isocyanates can also be usedsuch as 1,2-, 1,3- and 1,4-xylylene diisocyanates andm-tetramethylxylyene diisocyanate (TMXDI). Preferred aliphaticpolyisocyanates include hexamethylene-1,6-diisocyanate,2,2,4-trimethyl-hexamethylene-diisocyanate, and2,4,4-trimethyl-hexamethylene diisocyanate.

Specific examples of suitable cycloaliphatic polyisocyanates containfrom about 6 to about 20 carbon atoms and includecyclobutane-1,3-diisocyanate, 1,2-, 1,3- and 1,4-cyclohexanediisocyanates, 2,4- and 2,6-methylcyclohexane diisocyanate, 4,4′- and2,4′-dicyclohexyldiisocyanates, 1,3,5-cyclohexane triisocyanates,isocyanatomethylcyclohexane isocyanates, isocyanatoethylcyclohexaneisocyanates, bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4′- and2,4′-bis(isocyanatomethyl) dicyclohexane, isophorone diisocyanate, andthe like including derivatives, dimers, and trimers thereof. Preferredcycloaliphatic polyisocyanates include dicyclohexylmethane diisocyanateand isophorone diisocyanate.

Examples of suitable aromatic polyisocyanates contain from about 8 toabout 20 carbon atoms and include 2,4- and2,6-hexahydrotoluenediisocyanate, 1,2, 1,3, and 1,4-phenylenediisocyanates, triphenyl methane-4,4′, 4″-triisocyanate,naphthylene-1,5-diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI),2,4′-, 4,4′- and 2,2-biphenyl diisocyanates, 2,2′-, 2,4′- and4,4′-diphenylmethane diisocyanates (MDI), polyphenyl polymethylenepolyisocyanates (PMDI), mixtures of MDI and PMDI, mixtures of PMDI andTDI, and modified polyisocyanates derived from the above isocyanates andpolyisocyanates, including dimers and trimers thereof, or combinationsthereof.

Examples of suitable trialkoxysilylalkyl isocyanates includetrimethoxy-silylpropyl and triethoxysilylpropyl isocyanate.

The mole equivalent ratio of all NCO groups to all OH terminatedcompounds such as hydroxyl terminated thiocarbonates, the varioushydroxyl-terminated compounds such as polyols which are reacted with anisocyanate, the various dispersants, and the like is generally in excessso that chain extension subsequently can be carried out and generally isfrom about 1.0 or about 1.25 to about 5.0; desirably from about 1.4 toabout 2.2 and more desirably from about 1.4 to about 2.0 with respect towaterborne prepolymers and generally lower with respect to solvent bornesystems.

Ionic Dispersants, or Nonionic Dispersants, or Combinations Thereof

Various ionic or nonionic dispersants known to the art and to theliterature are generally utilized whenever a dispersion or a waterbornepolyurethane is desired. The ionic dispersants can be compounds whichcontain the following cations:

or compounds which contain the following anions: —SO₃ ⁻, —OSO₃ ⁻, —PO₂⁻, —PO₃ ⁻, —OPO₃ ⁻, or preferably —COO⁻. In addition, it should berecognized that the dispersing groups can be incorporated into thepolymer backbone using the thiocarbonate compounds in combination withthe previously described vinyl containing monomers that include anionic,cationic, and nonionic functional groups that are well-known to impartwater dispersability character to the polyurethane backbone. Examples ofsuch functional groups are carboxyl groups, sulfonic acid groups and thesalts thereof. Exemplary vinyl containing monomers that impart waterdispersability characteristics to the polyurethane backbone are acrylicand methacrylic acids and the metal or ammonium salts thereof. Thedispersing agent formed from the thiocarbonate typically would containhydroxyl functionality as described herein and can be prepared in aseparate synthesis reactor or in the same reactor as the prepolymer(just prior to the urethane synthesis or during urethane synthesis).

When ionic dispersants are utilized, desirably they are subsequentlyneutralized, that is some and up to all of the ionic dispersants areneutralized with the requirement that a stable dispersion be produced.The amount of the dispersants neutralized will vary depending upon thetype of the dispersant, the type of urethane polymer, and the like.

With regard to the various anionic dispersants, e.g. acid dispersants,which are preferred, such compounds generally contain a hydrophilicfunctional group such as a carboxyl or hydroxyl so that the urethane canbe dispersed into water, and may or may not be crosslinkable. Apreferred class of anionic dispersants include hydroxy-carboxylic acidshaving the general formula (HO)_(x)Q(COOH)_(y), wherein Q is a straightor branched hydrocarbon radical having 1 to 16 carbon atoms, and x and yare each, independently, 1 to 3, x preferably being 2 and y being 1.Examples of such hydroxy-carboxylic acids include citric acid,dimethylol propanoic acid (DMPA), dimethylol butanoic acid (DMBA),glycolic acid, thioglycolic acid, tartaric acid, dihydroxy tartaricacid, lactic acid, malic acid, dihydroxymalic acid. Dihydroxy-carboxylicacids are preferred with dimethylolpropanoic acid (DMPA) being mostpreferred. If desired, the carboxyl containing diol or triol may beincorporated into a polyester by reaction with a dicarboxylic acidbefore being incorporated into the polyurethane prepolymer. The typicalamount of such ionic dispersants when utilized can range from about 0.1to about 50 parts by weight in one aspect, from about 5 to about 30parts by weight in another aspect and from about 10 to 25 parts byweight in a further aspect, based upon the 100 parts by weight of theformed final polyurethane on a dry weight basis.

When preparing polyurethane dispersions according to the invention thedispersing groups can be derived from ionic polyester polyols, ionicpolyethers and polycarbonate polyols. For example, in ionic polyesterpolyols, the ionic character which these polyols exhibit is based on thecondensation of monomers which, in addition to the functional groupsrequired for the condensation (for example hydroxyl, amino and carboxylgroups), contain sulfonic acid, carboxylic acid and/or phosphonic acidgroups or sulfonate, carboxylate and/or phosphonate groups. A commercialexample of an ionic/ionizable polyol is Lexorez 1405-65 (carboxylic acidfunctional polyester polyols marketed by Inolex Chemical Company).

Nonionic dispersants include alkylene oxide compounds having repeatgroups either in the backbone, or in the side chain (preferred), orcombinations thereof. By the term “alkylene oxide” it is meant alkyleneoxide and substituted alkylene oxide compounds having from 2 to 10carbon atoms. Main chain nonionic dispersants generally have at leasttwo repeat groups and desirably at least several repeat groups betweenthe usually hydroxyl-terminated end groups of the oligomer or polymer. Apreferred anionic dispersant is polyethylene glycol.

The nonionic dispersants containing poly(alkylene oxide) side chains ifused in this invention in an amount to subsequently partially or fullyform a waterborne polyurethane; that is from about 0.1 to about 40 partsby weight and preferably about 5 to about 30 parts by weight, based uponthe 100 parts by weight of the formed final polyurethane on a dry weightbasis. At least about 50 wt. %, preferably at least about 70 wt. %, andmore preferably at least about 90 wt. % of the poly(alkylene oxide)side-chain units comprise poly(ethylene oxide), and the remainder of theside-chain poly(alkylene oxide) units can comprise alkylene oxide andsubstituted alkylene oxide units having from 3 to about 10 carbon atoms,such as propylene oxide, tetramethylene oxide, butylene oxides,epichlorohydrin, epibromohydrin, allyl glycidyl ether, styrene oxide,and the like, and mixtures thereof. The term “final polyurethane” meansthe polyurethane produced after formation of the prepolymer followed bythe chain extension step as described more fully hereafter.

Compounds of poly(alkylene oxide) side-chains are known to those skilledin the art. For example, active hydrogen-containing compounds includevarious diols having repeat units of poly(alkylene oxide) side-chains(e.g. from about 5 to about 50 and desirably from about 15 or about 20to about 30 or about 40) such as those described in U.S. Pat. No.3,905,929 (hereby incorporated herein by reference in its entirety).Further, U.S. Pat. No. 5,700,867 (hereby incorporated herein byreference in its entirety) teaches methods for incorporation ofpoly(ethylene oxide) side-chains at col. 4, line 35 to col. 5, line 45.A preferred active hydrogen-containing compound having poly(ethyleneoxide) side-chains is trimethylol propane monoethoxylate methyl ether,available as Tegomer D-3403 from Degussa-Goldschmidt. Tegomer D-3403generally has an average side chain degree of polymerization of fromabout 15 to about 35 and desirably from about 22 to about 28predominately ethylene oxide repeat units. The number average molecularweight of the preferred side-chain containing alkylene oxide monomers isgenerally from about 350 to about 5,000, and preferably from about 750to about 2,000.

Another class of nonionic dispersants include diisocyanates havingpendent polyoxyethylene chains which may be used in the preparation ofthe nonionic prepolymer include those described in the prior art, forexample in U.S. Pat. No. 3,920,598, hereby fully incorporated byreference. These diisocyanates, because of their function, may beregarded as dispersing diisocyanates. Particularly suitable dispersingdiisocyanates may be obtained by reacting two moles of an organicdiisocyanate in which the two isocyanate groups have differentreactivities with approximately one mole of a polyethylene glycolmono-ether, the initially formed urethane monoisocyanate then reactingat a higher temperature with the excess diisocyanate to form anallophanate diisocyanate having a pendent polyoxyethylene chain.

While either an ionic or a nonionic dispersant can be utilized, it iswithin the ambit of the present invention to utilize blends or mixturesof both ionic or nonionic dispersants, as well as a dispersant whichcontain an ionic and a nonionic group or segment to achieve desiredstable polyurethane dispersions.

Catalysts

Generally any conventional thermoplastic polyurethane catalyst known tothe literature and to the art can be utilized in preparing thethermoplastic polyurethane of the present invention. Such catalystsinclude organic and inorganic acid salts of, and organometallicderivatives of, bismuth, tin, iron, antimony, cobalt, thorium, aluminum,zinc, nickel, cerium, molybdenum, vanadium, copper, manganese andzirconium, as well as phosphines, tertiary organic amines, andmulti-functional polyalcohol amine catalysts. Representative organotincatalysts have from about 6 to about 20 carbon atoms and includestannous octoate, dibutyltin dioctoate, dibutyltin diluarate, and thelike. Representative tertiary organic amine catalysts includetriethylamine, triethylenediamine, N,N,N′N′-tetramethylethylenediamine,N,N,N′N′-tetraethylethylenediamine, N-methyl-morpholine,N-ethylmorpholine, N,N,N′,N′-tetramethylguanidine,N,N,N′,N′-tetramethyl-1,3-butanediamine, N,N-dimethylethanolamine,N,N-diethylethanol-amine, diazabicyclo[2.2.2]octane, and the like.Representative polyalcohol amine catalysts include triethanolamine,diethanolamine, or bis(2-hydroxyethyl)amino-2-propanol, and the like.

The amount of catalyst employed is generally less than about 1000 anddesirably less than about 400 parts by weight per million parts byweight of the total weight of the polyurethane forming reactants, i.e.,polyisocyanate(s), the hydroxyl-terminated thiocarbonates whether or notthey contain vinyl repeat units therein, and the chain extenders.Mixtures of the above noted catalysts can likewise be utilized. It isdesirable to use minimal amounts of the catalyst in order to minimizeside reactions. Preferred catalysts include stannous octoate, dibutyltindioctoate, dibutyltin dilaurate, and bismuth octoate.

Active Hydrogen Compounds or Isocyanate Reactive Compounds

Although optional, it is an important aspect of the invention thatactive hydrogen or isocyanate reactive compounds, such as polyols, canbe utilized in addition to the above-noted hydroxyl-terminatedthiocarbonates whether or not they contain vinyl or other repeat unitstherein. The use of such active hydrogen or isocyanate reactivecompounds is often desirable with regard to achieving suitablepolyurethane end properties and occasionally can serve as a dispersantor a quasi dispersant. The term “polyol” denotes any high molecularweight compound, other than the hydroxyl terminated thiocarbonatecompounds, polymers, and copolymers, such as polymers having an averageof about two or more hydroxyl groups per molecule. Examples of suchpolyols that can be used in the present invention include so-calledsimple or substantially polyhydroxyl hydrocarbon polyols (preferred), aswell as other polymeric polyols such as polyester polyols and polyetherpolyols, as well as polyhydroxy polyester amides, hydroxyl-containingpolycaprolactones, hydroxyl-containing acrylic interpolymers,hydroxyl-containing epoxides, polyhydroxy polycarbonates, polyhydroxypolyacetals, polyhydroxy polythioethers, polysiloxane polyols,ethoxylated polysiloxane polyols, polybutadiene polyols and hydrogenatedpolybutadiene polyols, polyacrylate polyols, halogenated polyesters orhalogenated polyethers, and the like, and mixtures thereof. Thepolyester polyols, polyether polyols, polycarbonate polyols, andpolysiloxane polyols are preferred.

The so-called hydrocarbon polyols are generally diols having from 2 toabout 12 or about 20 carbon atoms and preferably 2 to about 4 or about 6or about 10 carbon atoms and include ethylene glycol, 1,2- and1,3-propylene glycols, 1,2-, 1,3-, 1,4-, and 2,3-butylene glycols,hexane diols, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, andother glycols such as bisphenol-A, cyclohexane diol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol,2,2,4-trimethyl-1,3-pentanediol, halogenated diols, and the like, andmixtures thereof. Preferred diols include ethylene glycol, diethyleneglycol, propylene glycol, butylene glycol, hexane diol, and neopentylglycol.

The polyester polyols typically are esterification products prepared bythe reaction of organic polycarboxylic acids or their anhydrides with astoichiometric excess of a diol. The diols used in making the polyesterpolyols include alkylene glycols having from 2 to about 20 total carbonatoms, e.g., ethylene glycol, 1,2- and 1,3-propylene glycols, 1,2-,1,3-, 1,4-, and 2,3-butylene glycols, hexane diols, neopentyl glycol,1,6-hexanediol, 1,8-octanediol, and other glycols such as bisphenol-A,cyclohexane diol, cyclohexane dimethanol(1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol,2,2,4-trimethyl-1,3-pentanediol, diethylene glycol, triethylene glycol,tetraethylene glycol, polyethylene glycol, dipropylene glycol,polypropylene glycol, dibutylene glycol, polybutylene glycol, dimeratediol, hydroxylated bisphenols, polyether glycols, halogenated diols, andthe like, and mixtures thereof. Preferred diols include ethylene glycol,diethylene glycol, butylene glycol, hexane diol, and neopentyl glycol.Suitable carboxylic acids used in making the polyester polyols generallyhave from 1 to about 20 total carbon atoms and include dicarboxylicacids (preferred) and tricarboxylic acids and anhydrides, e.g., maleicacid, maleic anhydride, succinic acid, glutaric acid, glutaricanhydride, adipic acid (preferred), suberic acid, pimelic acid, azelaicacid, sebacic acid, chlorendic acid, 1,2,4-butane-tricarboxylic acid,phthalic acid, the isomers of phthalic acid, phthalic anhydride, fumaricacid, dimeric fatty acids such as oleic acid, and the like, and mixturesthereof.

The preferred polyester polyol has two hydroxyl end groups. Preferredpolyester diols include poly(butanediol adipate); hexane diol adipicacid and isophthalic acid polyesters such as hexane adipate isophthalatepolyester; hexane diol neopentyl glycol adipic acid polyester diols, andneopentyl glycol adipic acid.

Polythioether polyols which can be used include products obtained bycondensing thiodiglycol either alone or with other glycols, dicarboxylicacids, formaldehyde, aminoalcohols or aminocarboxylic acids.

Polyether diols may be substituted in whole or in part for the polyesterdiols. Polyether polyols contain from 2 to about 15 carbon atoms in therepeat unit and are obtained in known manner by the reaction of (A) thestarting compounds that contain reactive hydrogen atoms, such as wateror the diols set forth for preparing the polyester polyols, and (B)alkylene oxides, such as ethylene oxide, propylene oxide, butyleneoxide, styrene oxide, tetrahydrofuran, epichlorohydrin, and the like,and mixtures thereof. Preferred polyethers include poly(propyleneglycol), polytetrahydrofuran, and copolymers of poly(ethylene glycol)and poly(propylene glycol).

Polycarbonates include those obtained from the reaction of (A) diolssuch 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol,triethylene glycol, tetraethylene glycol, and the like, and mixturesthereof with (B) diarylcarbonates such as diphenylcarbonate or phosgene.

Polyacetals include the compounds that can be prepared from the reactionof (A) aldehydes, such as formaldehyde and the like, and (B) glycolssuch as diethylene glycol, triethylene glycol, ethoxylated4,4′-dihydroxy-diphenyldimethylmethane, 1,6-hexanediol, and the like.Polyacetals can also be prepared by the polymerization of cyclicacetals.

The aforementioned diols useful in making polyester polyols can also beused as additional reactants to prepare the isocyanate terminatedprepolymer.

Of the above various one or more polyols which can be utilized,generally the hydrocarbon polyols, polyether polyols, polyester polyols;and polyhydroxy polycarbonates are preferred. The above-noted optionalpolyols can be utilized in association with a hydroxyl-terminatedthiocarbonates in an amount of from about 0 or about 0.1 to about 80,desirably from about 1 to about 50 and preferably from about 2 to about20 parts by weight per 100 total parts by weight of the final formedpolyurethane.

Urethane Reaction Temperatures

The polyurethane forming reaction is performed at temperatures generallyfrom about 30° C. to about 220° C., desirably from about 40° C. to about120° C., and preferably from about 50° C. to about 100° C. Temperaturesabove about 220° C. are generally avoided in order to prevent thepolyurethanes from decomposing. Suitable mixing times in order to enablethe various components to react and form the thermoplastic polyurethanesof the present invention are generally from about 1 to about 5 anddesirably from about 2 to about 3 minutes.

Prepolymer and Polymer Preparation Routes

The preparation of a urethane prepolymer and/or polymer can generally becarried out according to one of three routes, that is a waterborneroute, a solvent route, or a bulk route.

Waterborne Route—Neutralization

Considering the waterborne route, one or more of the above noted ionicdispersants are utilized and the same must be neutralized generallybefore or during addition of the urethane prepolymer to water.Neutralization via the waterborne route involves, for example,converting the pendant carboxyl groups of an ionic (e.g. acid dispersantto a carboxylate anion, in the prepolymer, which has a waterdispersability enhancing effect. Suitable neutralizing agents for theprepolymers are desirably tertiary amines having a total of from 1 toabout 20 carbon atoms and desirably from about 1 to about 5 carbonatoms. Examples of suitable tertiary amines include triethyl amine(TEA), dimethyl ethanolamine (DMEA), N-methyl morpholine, and the like.Primary or secondary amines can also be used in lieu of tertiary aminesif they are sufficiently hindered to avoid interfering with the chainextension process. Alternatively, alkaline hydroxides such as sodiumhydroxide, potassium hydroxide, or ammonium hydroxide can be used.

A preferred neutralization route is to first neutralize the urethaneprepolymers containing an anionic dispersant therein and thensubsequently add the same to water. A less preferred route is to add theneutralizing compound such as a tertiary amine to water and then to addthe urethane prepolymer thereto. An amount of water is generallyutilized such that an aqueous dispersion of the urethane prepolymerexists. Thus, an amount of water can be utilized to obtain a desiredsolids content after chain extension and/or crosslinking via thewaterborne route such as from about 10 to about 70 and desirably fromabout 30 to about 55% by weight after chain extension.

Waterborne Route—Chain Extension

The active hydrogen-containing chain extender which is reacted with thewaterborne prepolymer is desirably an amine because of its high rate ofreactivity versus a diol or water, (which is a competing reaction).Suitable long-chain amines include polyester amides and polyamides, suchas the predominantly linear condensates obtained from reaction of (A)polybasic saturated and unsaturated carboxylic acids or theiranhydrides, and (B) polyvalent saturated or unsaturated aminoalcohols,diamines, polyamines, and the like, and mixtures thereof. Desired aminecompounds include an amino alcohol, ammonia, a primary or secondaryaliphatic, alicyclic, aromatic, araliphatic or heterocyclic amine havinga total of from about 2 to about 20 carbon atoms, especially a diamine,urea or derivatives thereof, hydrazine or a substituted hydrazine.Water-soluble chain extenders are preferred.

Examples of suitable chain extenders useful herein include ethylenediamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA),propylene diamine, butylene diamine. hexamethylene diamine,cyclohexylene diamine, piperazine, 2-methyl piperazine, phenylenediamine, 2-methylpentamethylenediamine, tolylene diamine, xylylenediamine, tris(2-aminoethyl) amine, 3,3′-dinitrobenzidine,4,4′-methylenebis (2-chloroaniline), 3,3′-dichloro-4,4′-bi-phenyldiamine, 2,6-diaminopyridine, 4,4′-diaminodiphenylmethane, menthanediamine, m-xylene diamine and isophorone diamine. Also materials such ashydrazine, azines such as acetone azine, substituted hydrazines such as,for example, dimethyl hydrazine, 1,6-hexamethylene-bis-hydrazine,carbodihydrazine, hydrazides of dicarboxylic acids and sulfonic acidssuch as adipic acid mono- or dihydrazide, oxalic acid dihydrazide,isophthalic acid dihydrazide, tartaric acid dihydrazide, 1,3-phenylenedisulfonic acid dihydrazide, and omega-amino-caproic acid dihydrazide.Hydrazides made by reacting lactones with hydrazine such asgamma-hydroxylbutyric hydrazide, bis-semi-carbazide, and bis-hydrazidecarbonic esters of glycols such as any of the glycols mentioned above,and the like.

Where the chain extender is other than water, for example a diamine orhydrazine, it may be added to the aqueous dispersion of prepolymer or,alternatively, it may already be present in the aqueous medium when theprepolymer is dispersed therein or added simultaneously.

The chain extension of the waterborne urethane prepolymers can beconducted at elevated, reduced or ambient temperatures. Convenienttemperatures are from about 5° C. to 95° C. or more, preferably fromabout 10° C. to about 45° C.

With respect to waterborne systems, the ratio of the total number ofequivalents of Zerewitinoff active hydrogen groups of all chainextenders utilized as compared to the total number of equivalents ofisocyanate groups ranges generally from about 0.1 to about 2.0,desirably from about 0.15 to about 1.5, and preferably from about 0.3 toabout 1.1. Of course, when water is utilized as a chain extender, theabove ratios are not applicable since as well known to the art and tothe literature, water can function both as a chain extender and adispersing medium and will be present in a large excess relative to theamount of free NCO groups.

Solvent Route

The various thermoplastic polyurethanes can be prepared bypolymerization of the various components, for example an isocyanatecompound, the hydroxyl terminated thiocarbonate, various active hydrogencompounds such as polyether diol, etc., and the like, in a solvent.Desired solvents include volatile hydrocarbons such as the variousalkanes having from 5 to about 17 carbon atoms, for example pentane,hexane, heptane, octane, and the like, or various aromatic orhydrocarbons containing both an aromatic ring and an aliphatic groupsuch as benzene, toluene, xylene, and the like. Another group ofsuitable solvents are the various acetates wherein the ester portioncontains from 1 to about 5 carbon atoms with examples including methylacetate, ethyl acetate, and the like. Various ketones having from about3 to about 10 carbon atoms can also be utilized such as acetone, methylethyl ketone, and the like. Polymerization of the various urethaneforming components such as the prepolymer components are carried out inthe solvent at suitable temperatures using suitable catalysts togenerally form a urethane prepolymer.

Solvent Route—Chain Extension

Chain extension of the various urethane prepolymers generally utilizeshydroxyl terminated chain extenders known to the literature and to theart such as various organic diols or glycols having a total of from 2 toabout 20 carbon atoms such as alkane diols, cycloaliphatic diols,alkylaryl diols, and the like. Alkane diols which have a total fromabout 2 to about 6 carbon atoms are often utilized with examplesincluding ethanediol, propane glycol, 1,6-hexanediol, 1,3-butanediol,1,5-pentanediol, neopentylglycol, and preferably 1,4-butanediol.Dialkylene ether glycols having from 4 to about 20 carbon atoms, canalso be utilized such as diethylene glycol and dipropylene glycol.Examples of suitable cycloaliphatic diols include 1,2-cyclopentanediol,1,4-cyclohexanedimethanol (CHDM) and the like. Examples of suitablealkylaryl diols include hydroquinone di(β-hydroxyethyl)ether(HQEE),1,4-benzenedimethanol, bisethoxy biphenol, bisphenol Aethoxylates, bisphenol F ethoxylates and the like. Still other suitablechain extenders are 1,3-di(2-hydroxyethyl)benzene, and1,2-di(2-hydroxyethoxy)benzene. Mixtures of chain extenders can also beutilized.

Suitable hydroxyl-functional chain extenders of the present inventioninclude 1,4-butanediol, ethylene glycol, diethylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol (CHDM), hydroquinonedi(β-hydroxyethyl)ether (HQEE), and 1,4-benzenedimethylol.

If an increase in molecular weight of the urethanes formed via a solventroute is desired, any residual isocyanate groups can be reacted withvarious diamines as set forth hereinabove with regard to the waterborneroute such as EA, DETA, or TETA, and the like. Alternatively,multi-functional chain extenders can be utilized such as trimethylolpropane, glycerol, pentaerythritol, 1,2,6-hexanetriol,N,N,N-triethanolamine, N,N-diethanolamine, trimethylolethane, anddiethylenetriamine. Combinations of chain extenders can be utilized. Theamount of multi-functional isocyanate components, e.g. multi-functionalchain extenders, catalysts, and/or polyols utilized to form thepolyurethanes is limited so that the polymer remains soluble and at areasonable processing and handling viscosity.

Bulk Polymerization Route

Another route to prepare the various thermoplastic urethane or urethaneprepolymers is via bulk polymerization such as in a reaction vessel oran extruder. According to this route, the various urethane formingcomponents such as the isocyanate reactive compounds, e.g. one or morepolyols, one or more thiocarbonate compounds, one or more chainextenders, one or more functional modifiers, and the like are mixedtogether along with one or more isocyanates and heated to a suitablereaction temperature to form a thermoplastic polyurethane composition.

Branched or precrosslinked urethane polymers are readily formed byutilizing polyisocyanates having 3 or 4 isocyanate groups and/or activehydrogen compounds such as the various above listed polyols having atleast three functional groups such as a hydroxyl group thereon. Chainextenders and/or various dispersants can also be utilized having 3, 4 ormore isocyanate reactive functional end groups. Such compounds are knownto the art and to the literature.

Thermoplastic Polyurethanes and Formation Routes Thereof

The thermoplastic polyurethanes of the present invention whetherprepared via a waterborne dispersion, a solution or bulk polymerizationcan be conducted by several different routes which are brieflysummarized and then more fully described. Polyurethanes are generallyformed by reacting 1) one or more isocyanates; 2) one or morehydroxyl-terminated thiocarbonate compounds, polymers, or copolymers; 3)optionally, one or more isocyanate reactive polyols; 4) optionally, oneor more chain extenders; and 5) optionally a catalyst.

A prepolymer route can be utilized wherein a hydroxyl terminatedthiocarbonate copolymer component containing repeat groups thereinderived from a conjugated diene and/or a vinyl monomer, optionally apolyol, and optionally a dispersant, are reacted with a polyisocyanateoptionally in the presence of a catalyst to form an isocyanateterminated prepolymer, which is subsequently chain extended. Thepolyurethane can either be solvent borne or waterborne. A second routerelates to a polyurethane prepolymer made by using various conjugateddiene and/or vinyl monomers as a diluent for the hydroxyl-terminatedthiocarbonated compound, polymer, or copolymer component, optionally apolyol, a dispersant, a polyisocyanate, and an optional catalyst are alladded together, mixed, and reacted. The polymer can be neutralized anddispersed in water and optionally chain extended. The vinyl and/or dienemonomers are then reacted into the backbone of the thiocarbonate in thepresence of an initiator. A third route relates to reacting a polyol anda dispersant (e.g., a waterborne acrylic) with a diisocyanate to form aprepolymer which is subsequently reacted with one or more thiocarbonatecompounds to form a thiocarbonate end capped urethane block. Similar toRoute 2, vinyl containing monomers can be utilized as reactive diluents.The prepolymer is then neutralized and dispersed into water. Variousvinyl monomers and/or conjugated diene monomers are then in situpolymerized to form block copolymers such as an ABA block copolymer, ifdesired.

Regardless of the reaction route, various vinyl and/or conjugated dienemonomers can exist as repeat units within the thiocarbonate compoundbefore it is reacted; or be initially contained within the mixture, orsubsequently added after formation of a dispersion and then reacted intothe backbone of the thiocarbonate compound.

Prepolymer Route

One polyurethane formation route involves a prepolymer route forpreparing a urethane-acrylic copolymer dispersion utilizing apolyacrylate polyol prepared from a hydroxyl functional thiocarbonatecompound previously described, an anionic dispersant, a polyisocyanate,and optionally a non-reactive organic solvent which can be utilized tocontrol the viscosity of the prepolymer. In this route, all of the abovedesired ingredients are added to reaction vessel and reacted with acatalyst optionally being added with the above ingredients or afterpartial reaction thereof. The prepolymer is subsequently neutralized asby an amine followed by the addition to/or of water. Chain extension canthen be carried out. This route utilizes a hydroxyl-terminatedthiocarbonate compound such as any of those set forth in Block FormulasAA, BB, CC, or EE where j equals 1 or 2 containing repeat groups derivedfrom the one or more conjugated dienes and/or the one or morevinyl-containing monomers such as vinyl acetates. Preferred conjugateddiene or vinyl compounds which can be utilized included styrene or anacrylate wherein the ester portion contains from 1 to about 10 carbonatoms such as ethylacrylate, butylacrylate, or 2-ethylhexylacrylate.

Various solvents can be utilized with organic solvents being desired asnoted above with N-methylpyrrolidone being preferred.

Optionally, one or more active hydrogen or isocyanate reactive compoundssuch as a polyol can be utilized. Such polyols are set forth hereinabovewith the hydrocarbon polyols, polyester polyols, polycarbonate polyols,and the polyether polyols such as tetramethyleneoxide polyol which ispreferred.

The isocyanate utilized to form a prepolymers is generally adiisocyanate as set forth hereinabove. Thus, generally any of theabove-noted aliphatic polyisocyanates, the cycloaliphaticpolyisocyanates, or the aromatic polyisocyanates can be utilized withthe cycloaliphatic polyisocyanates being preferred such asdicyclohexylmethane diisocyanate and isophorone diisocyanate.

The formation of the urethane-acrylic copolymer prepolymer is formed bycombining the above-noted compounds and heating at an elevatedtemperature such as from about 30° C. to about 100° C. and desirablyfrom about 40° C. to about 90° C. An excess of the polyisocyanate ispreferably utilized for subsequent chain extension. If a waterbornedispersion has been formed, desirably amine type chain extenders areutilized whereas if the prepolymer was formed by solutionpolymerization, diol type chain extenders are utilized. During theprepolymer formation, a urethane catalyst can be utilized as notedhereinabove or optionally, the prepolymer reaction can be partiallycarried out at which time a catalyst such as a tin catalyst can beadded.

Once the urethane dispersion derived from a thiocarbonate-vinylcopolymer has been formed, it can be chain extended utilizing any of theabove-noted chain extenders set forth herein with hydrazine beingpreferred. Alternatively, the chain extender can be contained in thewater which is preferable with aromatic isocyanate based prepolymers.

Various nuances of the above prepolymer dispersion route of forming apolyurethane derived from a thiocarbonate-acrylate copolymer can beutilized. For example, if a dispersion is not desired but only a solventborne urethane thiocarbonate-acrylic polymer, a neutralizing agent andwater is not utilized but only the above-noted solvents which are thenrequired in additional amounts to control the viscosity of the finalmolecular weight of the composition. Another option is that if apre-crosslinked polymer or copolymer is desired, it can be achieved by anumber of ways such as by utilizing a polyol, or an isocyanate, or evena chain extender having a functionality of at least three, alone or incombination with a difunctional chain extender. Crosslinking can also beachieved by post addition of crosslinkers.

The following examples with respect to the preparation of a polyurethanedispersion by essentially adding all of the components together servesto illustrate, but not to limit the present invention.

EXAMPLE 11

A prepolymer was prepared by combining all of the ingredients belowexcept the catalysts at 60° C. to a 4 neck flask equipped with athermometer, overhead stirrer and gas inlet. The temperature of thereaction mixture was raised to 84° C.-86° C. and held at thistemperature for 30 minutes. The catalyst was then added at 84° C.-86° C.and the temperature held there for another 1.5 hours or untiltheoretical NCO % was reached as indicated by titration of a smallsample. Material Parts-Wt

280 Dimethylolpropionic Acid 20.8 N-methylpyrrolidone 80 Isophoronediisocyanate 117 T9, tin di-octonate catalyst 0.1

A polyurethane dispersion was prepared by neutralizing the aboveprepolymer with 16.4 parts of triethylamine at 68° C. to 70° C. anddispersing the neutralized prepolymer in water while maintaining thewater/dispersion temperature below 28° C. The dispersed prepolymer wasextended with hydrazine to give a 40.4% solids polyurethane dispersionwith low sediment, a viscosity of 170 cps (at 25° C.) at a pH of 7.5.

EXAMPLE 12

The following is an example of the use of an acetone functional acrylicpolyol prepared from ethyl acrylate and diacetone acrylamide using theRAFT diol (dithiocarbonate based) to prepare a self-crosslinkingurethane-acrylic copolymer.

A prepolymer was prepared by combining all of the ingredients belowexcept the catalyst at 60° C. to a 4 neck flask equipped with athermometer, overhead stirrer and gas inlet. The temperature of thereaction mixture was raised to 84° C. to 86° C. and held at thistemperature for 30 minutes. The catalyst was then added at 84° C. to 86°C. and the temperature held there for another 1.5 hours or untiltheoretical NCO % was reached as indicated by titration of a smallsample. Material Parts-Wt

120 Tetramethyleneoxide polyol (OH# = 38.6) 120 Dimethylolpropionic Acid18.2 N-methylpyrrolidone 67 4,4′-methylene bis(cyclohexyl) diisocyanate117 T9, tin di-octonate catalyst 0.1

A polyurethane dispersion was prepared by neutralizing the aboveprepolymer with 14.4 parts of triethylamine at 68° C.-70° C. anddispersing the neutralized prepolymer in water while maintaining thewater/dispersion temperature below 28° C. The dispersed prepolymer wasextended with hydrazine to give a 43.6% solids polyurethane dispersionwith low sediment, a viscosity of 105 cps (at 25° C.) at a pH of 9.3. Tothis dispersion adipic acid dihydrazide (ADH) was added to render itself-crosslinking.

Prepolymer Route—“In-Situ” Acrylic Urethane Polymerization

Another route with regard to the preparation of a urethanethiocarbonate-vinyl copolymer comprises mixing all the various reactantcomponents together utilizing a conjugated diene and/or a vinyl monomersuch as an acrylate as a diluent, desirably with a dispersant andoptionally a polyol, and reacting the same with a isocyanate to form apolyurethane prepolymer. The composition is then neutralized with atertiary amine if required, dispersed in water, and generallysubsequently chain extended. Then, the diluent such as acrylate and/orstyrene monomers are polymerized into the thiocarbonate unit utilizing afree radical initiator. This route permits the size of the thiocarbonatevinyl block to be tailor made, permits formation of uniform highmolecular weight acrylate blocks, and desirable properties typicallyassociated with acrylic polymers such as weatherability, chemical andsolvent resistance, adhesion, and flexibility with respect to a desiredTg. Moreover, this approach is more economical in that a separate polyolpreparation step is not required and the monomer can act as a solventfor the prepolymer eliminating the need of processing solvents.

The preparation of the polyurethane dispersion using various monomerssuch as conjugated dienes or vinyl containing monomers as a diluent iscarried out utilizing many of the same components set forth hereinaboveas well as in the immediately above described urethane prepolymer routeand are hereby fully incorporated by reference. Hence, the procedurewill not be repeated herein.

An essential reaction component of the present route is the utilizationof a hydroxyl-terminated thiocarbonate discussed hereinabove such asthose set forth in Formulas AA, BB, CC, and EE wherein j equals 1 or 2and thus are fully incorporated by reference. As noted, thesethiocarbonates desirably do not have any units derived from a conjugateddiene or a vinyl monomer therein.

Any of the polyols previously described can optionally be utilized inthe prepolymer preparation.

Since a polyurethane dispersion is made, either an ionic or nonionicdispersant is utilized with the above noted acid dispersants beingpreferred such as the dihydroxy-carboxylic acids.

Rather than utilizing a solvent, various reactive monomers such as aconjugated diene monomer and/or one or more vinyl containing monomerssuch as the various acrylates are utilized as a diluent and the same canbe subsequently polymerized into the polyurethane to form the urethanethiocarbonate-vinyl copolymer. These monomers are set forth hereinaboveand are thus hereby incorporated by reference. The vinyl containingmonomers are desired with a styrene type and the acrylates ormethacrylates generally having from 1 to 18 carbon atoms in the esterportion being preferred.

The above noted various types of polyisocyanates are utilized withdiisocyanates being highly preferred such as the aliphaticpolyisocyanates, the cycloaliphatic polyisocyanates, aromaticpolyisocyanates, and the like with the cycloaliphatic polyisocyanatesbeing highly preferred.

The reaction of the various hydroxyl-containing components with thediisocyanates is carried out in a manner as set forth hereinaboveutilizing suitable urethane catalysts such as the various tin catalystsdescribed above. Naturally, an excess of the isocyanate is utilized sothat the polymers substantially contain isocyanate end groups forsubsequent reaction as by chain extending.

In order to form a dispersion, the active groups of the ionic typedispersants are neutralized and thus with regard to an acid dispersion,the same are neutralized using various basic compounds as notedhereinabove such as the various tertiary amines, ammonium hydroxide, andthe like. Generally neutralization is followed by or occurssimultaneously with addition of the neutralized polymer to water to forman aqueous dispersion of the urethane polymers.

The various diluent monomers are then polymerized utilizing free radicalinitiators as noted hereinabove such as various azo compounds,peroxides, peroxyesters, and the like. An important advantage of thepresent route is that the urethane thiocarbonate-acrylate copolymers canbe tailor made with regard to the size of the incorporated monomer suchas styrene or an acrylate by the amount thereof utilized as a diluentversus the raft (thiocarbonate) diol. Uniform block copolymers of thestyrene and/or the acrylate can thus be made. Hence, chemical andphysical properties of the end copolymer can also be controlled such ashardness, solvent resistance, functionality, and the like. Thepolyurethanes can possess the advantages of acrylic polymers such asweatherability, adhesion and resistant properties. The diluent monomerswhen polymerized are incorporated into the thiocarbonate compoundsbetween the sulfur atom and the adjacent

An example of such is Block Formula AA as is set forth hereinabove.Naturally, a portion of the urethane copolymer will contain a structureas set forth in Block Formulas AA, BB, CC, and EE where j equals 1 or 2.Preferred diluent monomers include styrene, an alkylacrylate, or analkylmethacrylate, wherein the alkyl has from 1 to about 30 carbon atomssuch as ethylacrylate, butylacrylate, and the like.

Nuances of the above general description of the preparation of apolyurethane dispersion utilizing various monomers as a diluent includesthe utilization of adding additional conjugated diene and/or vinylmonomer before polymerization, or after dispersing the urethaneprepolymer, particularly after chain extension. Thus, relatively lowviscosity dispersions can be prepared and then a desired amount ofadditional conjugated diene and/or vinyl type monomer such as acrylatecan be added to achieve desirable blocks within the thiocarbonate aswell as to achieve desired end properties. Another nuance is thatvarious crosslinking agents can be added either during or after chainextension to form a pre-crosslinked/branched product. When a solventborne urethane thiocarbonate-acrylic copolymer is desired, a dispersantis not utilized but rather one or more solvents which generally do notenter into the polymerization reaction. Such solvents are describedhereinabove and include compounds such as various alkanes, acetone,aromatic hydrocarbons, N-methylpyrrolidone, acetate amides such asdimethyl formamide, and the like.

The invention will be better understood by the following examples whichserve to illustrate but not to limit the present invention.

EXAMPLE 13

A prepolymer was prepared by adding all of the ingredients below exceptthe catalysts at 60° C. to a 4 neck flask equipped with a thermometer,overhead stirrer and gas inlet. The temperature of the reaction mixturewas raised to 84° C.-86° C. and held at this temperature for 30 minutes.The catalyst was then added at 84° C.-86° C. and the temperature heldthere for another 1.5 hours or until theoretical NCO % was reached asindicated by titration of a small sample. Material Parts-WtTetramethyleneoxide polyol (OH# = 38.6) 174.3

48.9 Dimethylolpropionic Acid 18.2 Methyl Methacrylate 111 ButylAcrylate 13 Isophorone diisocyanate 130.6 Tin di-octonoate catalyst 0.1

A polyurethane dispersion was prepared by neutralizing the aboveprepolymer with 16.4 parts of triethylamine at 68° C.-70° C. and thendispersing the neutralized prepolymer in water using high speed stirringwhile maintaining the water/dispersion temperature below 28° C. Withcontinued stirring the dispersed prepolymer was extended with hydrazine.Polymerization of the acrylic was effected by adding 0.3 parts of a 1%Fe (EDTA) solution, then adding 5 parts of a 2% erythorbic acid solutionneutralized with triethylamine then subsequently adding 3 parts of a3.5% t-butyl hydroperoxide solution and (heated at 34° C.-36° C.). Theresulting polymeric dispersion has a solids content of 46.5% with a lowlevel of sediment, a viscosity of 100 cps (at 25° C.) at a pH of 8.4.

EXAMPLE 14

The following is an example of the preparation of a “pure”urethane-acrylic copolymer (without other soft segment polyol based rawmaterials) using the RAFT diol and acrylic monomers to create thesoft-segment for the polyurethane.

A prepolymer was prepared by charging all of the ingredients below to a4 neck flask equipped with a thermometer, overhead stirrer and gasinlet. The temperature of the reaction mixture was raised to 84° C.-86°C. and held at this temperature for 2 hours. The temperature held untilthe theoretical NCO % was reached as indicated by titration of a smallsample. Material Parts-Wt

20.7 Butane diol 28.3 Dimethylolbutanoic Acid 27.0 Methyl methacrylate46 Butyl acrylate 184 Isophorone diisocyanate 153.9

A polyurethane dispersion was prepared by neutralizing the aboveprepolymer with 20.2 parts of triethylamine at 68° C.-70° C. and thendispersing the neutralized prepolymer in water using high speed stirringwhile maintaining the water/dispersion temperature below 28° C. Withcontinued stirring the dispersed prepolymer was extended with hydrazine.Polymerization of the acrylic was carried out by adding 0.3 parts of a1% Fe (EDTA) solution and 3 parts of a 3.5% t-butyl hydroperoxidesolution, heating to 34° C.-36° C. and then adding 5 parts of a 2%erythorbic acid solution neutralized with triethylamine. The resultingpolymeric dispersion has a solids content of 34.5% with a low level ofsediment, a viscosity of 50 cps (at 25° C.) at a pH of 7.5.

Thiocarbonate Capped Prepolymer Route

Still another polyurethane formation route relates to forming variousblock copolymers such as AB or (AB)_(n)A blocks containing at least onethiocarbonate or acrylic “A” block as well as at least one urethane “B”block, where n is from 1 to about 20 and desirably from 1 to about 5.This route generally involves the reaction of at least one polyol and ananionic dispersant and an excess amount of a diisocyanate to form apolyurethane prepolymer, in the presence of a conjugated diene or vinylmonomer diluent. Subsequently, the urethane prepolymer is reacted withone or more of the hydroxyl terminated thiocarbonate compounds set forthin Formulas AA, BB, CC, and EE where j equals 1 or 2, preferably 1, toproduce a polyurethane prepolymer generally having terminalthiocarbonate compounds containing no conjugated diene or vinyl repeatunits therein. The prepolymer is then neutralized and dispersed inwater. The various acrylate monomers can then be polymerized in situinto the terminal thiocarbonate compounds in the presence of freeradical initiators to yield a block copolymer such as an ABA wherein Ais the thiocarbonate-acrylate block and B is a polyurethane block.According to this route, the size and molecular weight of the variousblocks can be tailor made to yield suitable desired properties, such asmolecular weight, flexibility, and hardness. Other advantages includethe use of neutralizing agents which are more user friendly in that theyare less volatile and offensive than conventional neutralizing agentssuch as TEA. Still another advantage is that the urethane prepolymercontaining one or more thiocarbonate end groups can be stored,transported, moved to another location, or to an end user, etc., andoptionally dispersed, then one or more conjugated diene and/or vinylmonomers added thereto such as styrene or an acrylate and polymerizedinto the thiocarbonate compounds via in-situ free radicalpolymerization. Still another advantage of the thiocarbonate end groupcontaining urethane prepolymer is that different processes areavailable. For example, significantly higher prepolymer and watertemperatures with respect to the dispersion step can be utilized as wellas extended dispersion time (virtually unlimited) without loss ofisocyanate end groups due to water side reactions since, of course,there are no isocyanate groups. This route is also particularlyadvantageous for aromatic isocyanates that are harder to disperse andmore reactive towards water and typically leads to problems withsediment or dispersion quality. Generally, the thiocarbonate cappedprepolymer route yields increased productivity and process flexibilitywith less off-grade product.

The invention will be better understood by the following examples whichserve to illustrate but not to limit the present invention.

EXAMPLE 15

A prepolymer was prepared by combining all of the ingredients belowexcept the T9 and mono-hydroxyl functional RAFT reagent at 60° C. to a 4neck flask equipped with a thermometer, overhead stirrer and gas inlet.The temperature of the reaction mixture was raised to 84-86° C. and heldat this temperature for 30 minutes. The T9 catalyst was then added at84-86° C. and the temperature held there for another 1.5 hours. At thispoint the mono-hydroxyl functional RAFT reagent (DTC based) was added inan amount sufficient to cap the remaining isocyanate groups (asdetermined by titration) and the temperature held at 84-86° C. foranother hour or until less than 0.1% NCO was reached as indicated bytitration of a small sample. Material Parts Poly-tetramethylene oxide,1,000 number average 119.3 molecular weight (OH# = 38.6)Dimethylolbutanoic Acid 17.8 MMA 199.8 BA 66.6 4,4′-methylenebis(cyclohexyl) diisocyanate 94.2 T9, tin di-octonoate catalyst 0.1Mono-hydroxyl functional RAFT - Formula CC where 34.9 j = 1, R⁴ and R⁵are methyl, R⁶ and R⁷ are methyl, and R¹⁴ is ethylene

A polyurethane dispersion was prepared by neutralizing the aboveprepolymer with 12.7 parts of triethylamine at 68-70° C. and thendispersing the neutralized prepolymer in de-ionized water using highspeed stirring. Polymerization of the acrylic was effected by adding 0.5parts of a 1% Fe(EDTA) solution and 3 parts of a 3.5% t-butylhydroperoxide solution, heating to 34-36° C. and then adding 5 parts ofa 2% erythorbic acid neutralized with triethylamine. The resultingpolymeric dispersion has a solids content of 43.7% with a low level ofsediment, a viscosity of 230 cps (at 25° C.) at a pH of 7.7.

EXAMPLE 16

A prepolymer was prepared by combining all of the ingredients belowexcept the mono-hydroxyl functional RAFT reagent at 60° C. to a 4 neckflask equipped with a thermometer, overhead stirrer and gas inlet. Thetemperature of the reaction mixture was raised to 45-50° C. and held atthis temperature for 30 minutes. The temperature was then raised to70-75° C. and held there for another 1.5 hours. At this point themono-hydroxyl functional RAFT reagent (DTC based) was added in an amountsufficient to cap the remaining isocyanate groups (as determined bytitration) and the temperature held at 70-75° C. for another hour oruntil theoretical NCO % was reached as indicated by titration of a smallsample. Material Parts PPG 2025 polyol (OH# = 56) (polypropylene glycolpolyol) 119.3 Dimethylolbutanoic Acid 17.8 MMA 64.3 BA 192.84,4′-diphenyl-methylene diisocyanate (MDI, Mondur M) 60.9 Mono-hydroxylfunctional RAFT reagent - Formula CC 30.2 where j = 1, R⁴ and R⁵ aremethyl, R⁶ and R⁷ are methyl, and R¹⁴ is ethylene

A polyurethane dispersion was prepared by neutralizing the aboveprepolymer with 12.7 parts of triethylamine at 68-70° C. (typically notfeasible with aromatic isocyanate based prepolymers containing activeNCO groups) and then dispersing the neutralized prepolymer in de-ionizedwater using high speed stirring while maintaining the water/dispersiontemperature. After the prepolymer was dispersed, 7 parts of di-acetoneacrylamide dissolved in 7 parts de-ionized water was added to thedispersion. Polymerization of the acrylic was effected by adding 0.3parts of a 1% Fe(EDTA) solution and 2.5 parts of a 2% erythorbic acidneutralized with triethylamine 3.5% t-butyl hydroperoxide solution,heating to 38-40° C. and then adding 1.4 parts of a 3.5% t-butylhydroperoxide solution. The resulting polymeric dispersion has a solidscontent of 31.3% with a low level of sediment, a viscosity of 30 cps (at25° C.) at a pH of 7.6. Adipic acid dihydrazide can be added to thedispersion to render it self crosslinking.

EXAMPLE 17

A similar polyurethane dispersion was prepared to the previouslydescribed dispersion (Example 6) using the same prepolymer composition,but neutralizing the above prepolymer with 11.2 parts of Di-methylethanol amine at 68-70° C. (typically not feasible with aromaticisocyanate based prepolymers containing active NCO groups) and thendispersing the neutralized prepolymer in de-ionized water using highspeed stirring while maintaining the water/dispersion temperature. Afterthe prepolymer was dispersed, 7 parts of di-acetone acrylamide dissolvedin 7 parts de-ionized water was added to the dispersion. Polymerizationof the acrylic was effected by adding 0.3 parts of a 1% Fe(EDTA)solution and 2.5 parts of a 2% erythorbic acid solution neutralized withtriethylamine 3.5% t-butyl hydroperoxide solution, heating to 38-40° C.and then adding 1.4 parts of a 3.5% t-butyl hydroperoxide solution. Theresulting polymeric dispersion has a solids content of 31.8% with a lowlevel of sediment, a viscosity of 110 cps (at 25° C.) at a pH of 8.0.Adipic acid dihydrazide can be added to the dispersion to render it selfcrosslinking.

Other Prepolymer Routes

Any of the above described preparation routes of course can be used incombination to attain particular results or combine the practicalbenefits of each. For example, an acrylic polyol can be preparedaccording to the first or prepolymer route and used as a component inthe second or in-situ urethane-acrylic preparation route for thesynthesis of the copolymer. While the above three basic routes have beenutilized with respect to preferred embodiments of the present invention,it is to be understood that any of the other routes can also beutilized.

Polyurethane—Molecular Weight

The number average molecular weight of the polymerized thermoplasticpolyurethanes of the present invention made by the various routes canbroadly range from about 10,000 to about 2,000,000. In another aspectthe number average molecular weight can range from about 20,000 to about1,500,000, and in still another aspect from about 40,000 to about500,000, unless crosslinked. The molecular weight of the polymers of theinvention is measured by gel permeation chromatography (GPC) using apolystyrene standard of known molecular weight as a calibrationstandard. The overall equivalent ratio of all NCO groups to all OHgroups, i.e. NCO/OH is generally from about 0.1 to about 10, desirablyfrom about 0.4 to about 4 and preferably from about 0.8 to about 2.2.

Additives, Etc.

In addition to the above-identified components, the polyurethanecompositions of the present invention can also contain variousadditives, fillers, lubricants, UV absorbers, waxes, antioxidants,wetting agents, surfactants, thickening agents and the like, which canbe utilized in conventional amounts as known to the art and to theliterature. The additives utilized generally impart desired propertiesto the thermoplastic polyurethanes. Examples of fillers include talc,silicates, clays, calcium carbonate, and the like. If it is desired thatthe polyurethane compositions of the present invention have a color orhue, any conventional pigment or dye can be utilized in conventionalamounts. Hence, any pigment known to the art and to the literature canbe utilized as for example titanium dioxide, iron oxide, carbon black,and the like, as well as various dyes provided that they do notinterfere with or are added after the urethane reactions are essentiallycomplete.

Thermoset or crosslinked polymers can be obtained by usingmulti-functional crosslinking agents customary in the industry, such as,for example, water-soluble or water-emulsifiable melamine orbenzoguans/nine resins, low viscosity polyisocyanates,polycarbodiimides, water-emulsifiable polyisocyanates orwater-emulsifiable prepolymers having terminal isocyanate groups,water-soluble or water-dispersible polyaziridines, poly-epoxy functionalcompounds, epoxy-silanes and blocked polyisocyanates, which can be addedduring formulation of water-dilutable coatings, adhesives and sealantsusing the polyacrylic-urethane dispersions according to the invention.

The thiocarbonate-polyurethane polymers of the present invention,generally regardless of route preparation, have good properties such astoughness, abrasion resistance, good cold flexibility, excellenthydrolytic stability, good UV weatherability, good heat stability, aswell as good oxidative stability and chemical resistance. However,desirably the thiocarbonyl groups are deactivated before any end use.The amount of the various vinyl monomers such as acrylate or styreneutilized will also affect the physical properties and low amount ofvinyl monomers such as the various acrylates with high amounts of thethiocarbonate compounds can be utilized, or visa versa.

Utility

The bulk thermoplastic polyurethanes can be extruded into any desiredend product or form, or can be cooled and pelletized or granulated forstorage or bulk shipping. The extrudate can be immediately processed inany manner such as molding, injection molding, calendaring, etc.

The polyurethane dispersions obtained by the method of the invention canbe employed as coating compositions and may be applied to any substrateincluding wood, metals, glass, cloth, leather, paper, plastics, foam andthe like, by any conventional method including brushing, dipping, flowcoating, spraying and the like. Films obtained from the coatingcompositions can be used as adhesives in the production of compositearticles.

Coatings with regard to various wood substrates are preferred. However,the polyurethanes can also be used to coat fabrics, either woven ornon-woven and made from polyester fibers, polyolefin fibers, nylonfibers, or natural fibers and the like. Industrial applications includecoated films, sheets, or fabrics as for conveyer belts, containers,collapsible storage bags (e.g., fuel, water, fruit juices, food oils,heating oils etc), inflatables (e.g., escape slides and platforms,flotation devices, air-mattresses, life jackets, white-water or liferafts, oil booms, petro-seals, power lifting devices, weather balloons)or grape press membranes, and the like.

In the apparel industry, uses include labels and stickers used inlaundry and professional outfits, as well as protectiveclothing/apparel, protective covers, rainwear, sealable coatings forlabels, surgical drapes, protective apparel, synthetic leather, tents,upholstery, wet or diving suits, and the like. Other uses include linersfor pipe repair, load space covers, and the like or any applicationwhere melt processable materials are used. The polyurethanes are alsouseful is sealant, caulking, adhesive, and other elastomericapplications.

An important area of use of the waterborne polyurethane dispersions ofthe present invention is in the personal care field and cosmetic fieldsuch as for film formers to provide water or moisture resistance,luster, better spreadability of solutions, and the like. Suchdispersions can be incorporated as a component thereof into personalcare products such as daily skin care products (cosmetics, lip balms,moisturizers, eye-lash liners, lipsticks, lip balms, sunscreens, and thelike), as well as nail care products, hair care products, and the like.Such personal care products can be lotions, gels, sprays, sticks,compressed liquids, liquid suspensions, and the like. The urethanedispersions of the present invention are especially suitable as hairfixatives, nail polish, and the like.

Personal care compositions can include the waterborne polyurethanedispersions of this invention, mixed and optionally reacted further witha topically acceptable phase. The term “topically acceptable phase”means any combination of optional liquid or solid ingredients suitablefor a desired personal care composition in combination with (andsometimes reacted with) the plasticized waterborne polyurethanedispersions described heretofore. Such optional ingredients can compriseone or more of a wide variety of components well known to those skilledin the art, such as chelators, conditioners, diluents, fragrances,humectant skin or hair conditioners, lubricants, moisturebarriers/emollients, neutralizers, opacifiers, pharmaceutical actives,preservatives, solvents, spreading aids, sunscreens, surfactants,conditioning polymers, vitamins, viscosity modifiers/emulsifiers, andthe like, as well as numerous other optional components for enhancingand maintaining the properties of the personal care compositions.Exemplary skin care compositions utilizing such components include thoseof U.S. Pat. Nos. 5,073,372, 5,380,528, 5,599,549, 5,874,095, 5,883,085,6,013,271, and 5,948,416, all incorporated herein by reference. Suchcomponents are also described in detail in well known references such asMitchell C. Schlossman, The Chemistry and Manufacture of Cosmetics,Volumes I and 11, Allured Publishing Corporation, 2000.

The polyurethanes can also be used to make unsupported TPU film andsheet via extrusion or calendering. Applications for such films andsheets include air mattresses, shower curtains, aeration sheets forwater purification plants, adhesives, equipment covers, protective wear,aprons, body bags, tank liners, pipe liners, and the like. Thepolyurethanes can be formed into articles comprising films, membranes orsheets which range generally from about 0.25 or about 0.50 mils to about10 mils (about 6.35 or about 12.7 to about 254 micrometers), andpreferably from about 1 mil to about 4 mils (about 25.4 to about 101.6micrometers).

While in accordance with the patent statutes the best mode and preferredembodiment have been set forth, the scope of the invention is notintended to be limited thereto, but only by the scope of the attachedclaims.

1. A polyurethane, comprising: a polymer containing at least one repeatunit derived from an isocyanate compound and at least one repeat unitderived from a hydroxyl-terminated thiocarbonate containing compound,said thiocarbonate containing compound having the formula:

wherein, in the above formulas: each R¹ and R², independently, is alinear or branched alkyl having from 1 to about 6 carbon atoms, or asubstituted C₁ to about C₆ alkyl having one or more substituents, or oneor more aryls, or a substituted aryl having from 1 to 6 substituents onthe aryl ring; wherein said one or more substituents, independently,comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or ahalogen which can be the same or different, or a cyano, or an etherhaving a total of from 2 to about 20 carbon atoms, or a nitro, orcombinations thereof; or wherein R¹ and R² are part of a cyclic ringhaving from about 5 to about 12 total carbon atoms; R³ is benzyl, a C₁through C₁₈ alkyl, or a substituted C₁ to C₁₈ alkyl wherein saidsubstituted group is halogen, hydroxyl, or alkoxy, or a C₁ to C₁₈hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl,carboalkoxyalkyl, or mercaptoalkyl, each R⁴ and R⁵, independently, isoptionally substituted, and is a linear or branched alkyl having from 1to about 12 carbon atoms; or an aryl having from 6 to about 18 carbonatoms, optionally containing heteroatoms; or wherein said R⁴ and said R⁵substituents, independently, comprise an alkyl having from 1 to 6 carbonatoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20carbon atoms, a nitro, or combinations thereof, or R⁴ and R⁵ can form asubstituted or unsubstituted cyclic ring having from 3 to about 12carbon atoms; wherein R⁶ and R⁷, independently, is optionallysubstituted and optionally contains heteroatoms; and is hydrogen; alinear or branched alkyl having from 1 to about 18 carbon atoms, an arylhaving from 6 to about 18 carbon atoms optionally saturated orunsaturated; an arylalkyl having from about 7 to about 18 carbon atoms;an alkenealkyl having from 3 to about 18 carbon atoms; or is derivedfrom a polyalkylene glycol ether having from 3 to about 200 carbonatoms; or is derived from piperazine, morpholine, pyrrolidone,piperidine, 4-alkyl amino-2,2,6,6-tetramethyl piperidine,1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine,phenothiazine, iminodibenzyl, phenoxazine,N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivativesthereof; or R⁶ and R⁷ can form a substituted or unsubstituted cyclicring having a total of from 4 to about 12 carbon atoms; and wherein saidsubstituents, independently, are the same as R¹³; R¹³ is optionallysubstituted, and is a linear or branched alkyl or alkylene having from 1to about 12 carbon atoms, an aryl optionally saturated or unsaturated;an arylalkyl having from about 7 to about 18 carbon atoms; an acyl; analkene group; an alkenealkyl having from 3 to about 18 carbon atoms; analkylene group; an alkoxyalkyl derived from a polyalkylene glycol orderived from a polyalkylene glycol monoalkyl ether having from about 3to about 200 carbon atoms or derived from a polyalkylene glycol monoarylether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;a phosphorous containing alkyl; or a substituted or unsubstituted arylring containing heteroatoms; wherein the R¹³ substituents comprise analkyl having from 1 to 6 carbon atoms; an aryl; a halogen such asfluorine or chlorine; a cyano group; an amino group; an alkene group; analkoxycarbonyl group; an aryloxycarbonyl group; a carboxy group; anacyloxy group; a carbamoyl group; an alkylcarbonyl group; analkylarylcarbonyl group; an arylcarbonyl group; an arylalkylcarbonylgroup; a phthalimido group; a maleimido group; a succinimido group;amidino group; guanidimo group; allyl group; epoxy group; alkoxy group;an alkali metal salt; a quaternary ammonium salt; a hydroxyl group; anether having a total of from 2 to about 20 carbon atoms; a nitro;sulfur; phosphorous; a carboalkoxy group; a heterocyclic groupcontaining one or more sulfur, oxygen or nitrogen atoms, or combinationsthereof; each R¹⁴ is derived from a polyol, wherein said polyolcomprises a hydrocarbon polyol wherein R¹⁴ comprises an alkyl or analkylene group, or a substituted alkyl or alkylene group having from 2to about 200 carbon atoms, and wherein said substituted alkyl oralkylene group comprises oxygen, or a halogen; polyester polyol,polyether polyol, polyhydroxy polyester amide, hydroxyl-containingpolycaprolactone, hydroxyl-containing acrylic interpolymer,hydroxyl-containing epoxide, polyhydroxy polycarbonate, polyhydroxypolyacetal, polyhydroxy polythioether, polysiloxane polyol, ethoxylatedpolysiloxane polyol, polybutadiene polyol, hydrogenated polybutadienepolyol, polyacrylate polyol, halogenated polyester polyol, orhalogenated polyether polyol, or combinations thereof; wherein T is adivalent radical having a nitrogen atom directly attached to a carbonatom of the thiocarbonyl group; and wherein said m and said n,independently, is from about 1 to about 10,000; wherein said conjugateddiene monomer has from 4 to about 12 carbon atoms; wherein said vinylmonomer has the formula

where R¹⁵ comprises hydrogen, halogen, C₁ to C₄ alkyl, or substitutedC₁-C₄ alkyl wherein the substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR¹⁷), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc, or an ammonium salt,acyloxy, aroyloxy(O₂CR¹⁷), alkoxy-carbonyl(CO₂R¹⁷), or aryloxy-carbonyl;wherein R¹⁶ comprises hydrogen, R¹⁷, CO₂H, CO₂R¹⁷, COR¹⁷, CN, CONH₂,CONHR¹⁷, O₂CR¹⁷, OR¹⁷, or halogen; R¹⁷, independently, comprises C₁-C₁₈alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl, heterocyclyl,aralkyl, or alkaryl, wherein the substituents independently comprise oneor more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts),sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato,cyano, silyl, halo and dialkylamino; or wherein said vinyl containingmonomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide,N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;styrene, a methyl styrene, C₁,-C₁₂ alkyl styrenes with substitute groupsboth either on the chain or on the ring, or combinations thereof.
 2. Thepolyurethane according to claim 1, wherein said polymer comprises atleast one repeat unit derived from at least one of the following: anionic dispersant, or a nonionic dispersant, or combinations thereof; oran active hydrogen compound capable of reacting with said mono or saidpolyisocyanate, said active hydrogen compound comprising a hydrocarbonpolyol having a total of from 2 to about 20 carbon atoms, a polyesterpolyol, a polyether polyol, polyhydroxy polyester amides,hydroxyl-containing polycaprolactone, hydroxyl-containing acrylicinterpolymer, hydroxyl-containing epoxide, polyhydroxy polycarbonate,polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol,ethoxylated polysiloxane polyol, polybutadiene polyol and hydrogenatedpolybutadiene polyol, polyacrylate polyol, halogenated polyester polyolor halogenated polyether polyol, or combinations thereof; or a chainextender.
 3. The polyurethane according to claim 2, wherein T is

wherein R⁸ and R⁹, independently, is optionally substituted and ishydrogen, a linear or branched alkyl having from 1 to about 18 carbonatoms, an aryl group having from about 6 to about 18 carbon atoms, anarylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl havingfrom 3 to about 18 carbon atoms, wherein the substituents can be thesame as described herein for R¹ and R². wherein R¹⁰ is optionallysubstituted, or is non-existent, or an alkylene group having from 1 toabout 18 carbon atoms with about 1 to about 6 carbon atoms preferred, orderived from a polyalkylene glycol ether having from 3 to about 200carbon atoms, wherein the substituents can be the same as describedherein for R¹ and R² or are hereroatoms such as oxygen, nitrogen, sulfuror phosphorous; and wherein R¹¹ and R¹², independently, is an alkylenegroup having from 1 to 4 carbon atoms, and wherein R¹¹ and R¹²,independently, is optionally substituted and wherein said substituentsare, independently, the same as for R¹ and R²; wherein said isocyanatecompound comprises an aliphatic, a cycloaliphatic, or an aromaticpolyisocyanate, or combinations thereof; wherein said dispersantcomprises a side-chain containing alkylene oxide monomer wherein saidalkylene oxide side chain units have from 2 to about 10 carbon atoms andare unsubstituted, substituted, or both unsubstituted and substitutedwith at least about 50 wt. % of said alkylene oxide groups beingethylene oxide; or said dispersant monomer has the formula(HO)_(x)Q(COOH)_(y), wherein Q is a straight or branched hydrocarbonradical having 1 to 12 carbon atoms, and wherein x and y are 1 to 3; orwherein said dispersant is derived from a diisocyanate comprising apendant polyoxyethylene chain, or wherein said chain extender is anamine containing chain extender, or an organic diol chain extender. 4.The polyurethane according to claim 3, wherein said active hydrogenhydrocarbon polyol is a diol having from 2 to about 20 carbon atoms,wherein said polyester polyol is derived from an organic polycarboxylicacid or an anhydride thereof having from 1 to about 20 carbon atoms anda diol having from 2 to about 20 carbon atoms, wherein said polyetherpolyol has from 2 to about 15 carbon atoms in the repeat group, andwherein said polycarbonate is derived from a diol and a diarylcarbonate,and wherein said amine containing chain extender comprises ethylenediamine (EA), diethylene triamine (DETA), triethylene tetramine (TETA),propylene diamine, butylene diamine. hexamethylene diamine,cyclohexylene diamine, piperazine, 2-methyl piperazine, phenylenediamine, tolylene diamine, xylylene diamine, tris(2-aminoethyl) amine,3,3′-dinitrobenzidine, 4,4′-methylenebis (2-chloroaniline),3,3′-dichloro-4,4′-bi-phenyl diamine, 2,6-diaminopyridine,4,4′-diaminodiphenylmethane, menthane diamine, m-xylene diamine,isophorone diamine, hydrazine, azine, substituted hydrazine, a hydrazineof dicarboxylic acid or sulfonic acid, and wherein said organic diolchain extender is an aliphatic diol, a cycloaliphatic diol, or analkylaryl diol having a total of from about 2 to about 20 carbon atoms,or a dialkylene ether glycol having from 4 to about 20 carbon atoms, orcombinations thereof.
 5. The polyurethane according to claim 4, whereinsaid diene monomer is 1,3-butadiene, isoprene, 1,3-pentadiene,2,3-dimethyl-1-3-butadiene, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene, or combinations thereof; wherein said vinylmonomer is methyl methacrylate, ethyl methacrylate, propyl methacrylate(all isomers), butyl methacrylate (all isomers), 2-ethylhexylmethacrylate, isobornyl methacrylate, methacrylic acid, benzylmethacrylate, phenyl methacrylate, methacrylonitrile,alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate(all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate,isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate,acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethylmethacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutylmethacrylate (all isomers), N,N-dimethylaminoethyl methacrylate,N,N-diethylaminoethyl methacrylate, triethyleneglycol methacrylate;itaconic anhydride, itaconic acid; sodium and zinc salts; itaconic acidand 2-acrylamido-2-methyl-1-propanesulfonic acid; N-vinylimidazole,vinylpyridine N-oxide, 4-vinylpyridine carboxymethylbetaine, diallyldimethylammonium chloride, p-styrenesulfonic acid, p-styrenecarboxylicacid, 2-dimethylaminioethyl acrylate and its alkyl or hydrogen halidesalts, 2-dimethyl-aminoethyl methacrylate and its alkyl or hydrogenhalide salts, N-(3-dimethyl-aminopropyl)acrylamide,N-(3-dimethylaminoproyl)methacrylamide, diacetone acrylamide,2-(acetoacetoxy)ethyl methacrylate, 2-(acryloyloxy)ethyl acetoacetate,3-trialkoxysilylpropylmethacrylate (methoxy, ethoxy, isopropoxy),glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (allisomers), hydroxybutyl acrylate (all isomers), N,N-diethylaminoethylacrylate, triethyleneglycol acrylate, methacrylamide,N-methylacrylamide, N,N-dimethyl-acrylamide, N-tertbutylmethacrylamide,N—N-butylmethacrylamide, N-methylol-methacrylamide,N-ethylolmethacrylamide, N-tertbutylacrylamide, N—N-butyl-acrylamide,N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (allisomers), diethylaminostyrene (all isomers), alpha-methylvinyl benzoicacid (all isomers), diethylamino alpha-methylstyrene (all isomers),p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic sodium salt,trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate,tributoxysilylpropyl methacrylate, dimethoxy-methylsilylpropylmethacrylate, diethoxymethylsilylpropyl methacrylate,dibutoxy-methylsilylpropyl methacrylate, diisopropoxymethylsilylpropylmethacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropylmethacrylate, dibutoxy silylpropyl methacrylate, diisopropoxysilylpropylmethacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropylacrylate, tributoxysilylpropyl acrylate, dimethoxy-methylsilylpropylacrylate, diethoxymethylsilylpropyl acrylate, dibutoxy-methylsilylpropylacrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxy-silylpropylacrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate,diisopropoxysilylpropyl amiate, vinyl acetate, vinyl butyrate, vinylbenzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleicanhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone,N-vinylcarbazole, butadiene, isoprene, chloroprene, ethylene, andpropylene; wherein each said m and n is from about 5 to about 500;wherein, in each formulation, each R¹ and R², independently, is methyl,or phenyl; wherein each said R³, independently, is an alkyl having from1 to about 18 carbon atoms; wherein each said R⁴ and R⁵, independently,is methyl or phenyl; wherein each said R⁶ and R⁷, independently, is aphenyl, an alkyl or a substituted alkyl having from 1 to about 18 carbonatoms; wherein each said R¹³, independently, is an alkyl or an alkylenehaving from 1 to about 6 carbon atoms; wherein said isocyanate compoundis said polyisocyanate, wherein said aliphatic polyisocyanate has atotal of from 5 to about 20 carbon atoms, wherein said cycloaliphaticpolyisocyanate contains from about 6 to about 20 carbon atoms, andwherein said aromatic polyisocyanate contains from about 8 to about 20carbon atoms; wherein said dispersant is an anionic dispersant, andwherein said (HO)_(x)Q(COOH)_(y) dispersant comprises citric acid,dimethylol propanoic acid (DMPA), dimethylol butanoic acid (DMBA),glycolic acid, thioglycolic acid, tartaric acid, dihydroxy tartaricacid, lactic acid, maleic acid, dihydroxymalic acid, or combinationsthereof.
 6. The polyurethane according to claim 5, wherein saidconjugated diene monomer is butadiene, isoprene, or combinationsthereof; and wherein said vinyl monomer is a C₁-C₁₈ acrylate; acrylicacid; C₁-C₈ monoalkyl and dialkyl acrylamide; a combination of C₁-C₈acrylate and methacrylate; a combination of said acrylamide and C₁-C₈monoalkyl and dialkyl methacrylamide; wherein said R¹⁴ polyol is saidsubstantially hydrocarbon polyol and wherein said alkyl or alkylenegroup, or said substituted alkyl or alkylene group has from 2 to about10 carbon atoms; wherein said aliphatic polyisocyanate comprisestetramethylene diisocyanate, hexamethylene-1,6-diisocyanate (HDI),decamethylene diisocyanate, 1,12-dodecane diisocyanate,2,2,4-trimethyl-hexamethylene diisocyanate,2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, or combinations thereof, wherein said cycloaliphaticpolyisocyanate comprises cyclobutane-1,3-diisocyanate, 1,2-, 1,3- and1,4-cyclohexane diisocyanates, 2,4- and 2,6-methylcyclohexanediisocyanate, 4,4′- and 2,4′-dicyclohexyldiisocyanates,1,3,5-cyclohexane triisocyanates, isocyanatomethylcyclohexaneisocyanates, isocyanatoethylcyclohexane isocyanates,bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4′- and2,4′-bis(isocyanatomethyl) dicyclohexane, isophorone diisocyanate,derivatives, dimers, or trimers thereof, or combinations thereof;wherein said aromatic polyisocyanate comprises 2,4- and2,6-hexahydrotoluenediisocyanate, 1,2, 1,3, and 1,4-phenylenediisocyanates, triphenyl methane-4,4′,4″-triisocyanate,naphthylene-1,5-diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI),2,4′-, 4,4′- and 2,2-biphenyl diisocyanates, 2,2′-, 2,4′- and4,4′-diphenylmethane diisocyanates (MDI), polyphenyl polymethylenepolyisocyanates (PMDI), mixtures of MDI and PMDI, mixtures of PMDI andTDI, aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylylenediisocyanates and m-tetramethylxylyene diisocyanate (TMXDI), or modifiedpolyisocyanates thereof including dimers and trimers, or combinationsthereof; wherein said anionic dispersant is trimethylol propanemonoethoxylate methyl ether, DMPA, or DMBA, or combinations thereof; andwherein said active hydrogen compound is said hydrocarbon diol, saidpolyester diol, said polyether diol, or said polycarbonate diol.
 7. Thepolyurethane according to claim 6, wherein said diisocyanate isdicyclohexyl methane diisocyanate, isophorone diisocyanate, MDI, orPMDI, or combinations thereof; wherein said active hydrogen compound issaid hydrocarbon polyol having from 3 to about 6 carbon atoms,poly(propylene glycol)tetramethylene oxide polyol, polytetrahydrofurandiol, or polypropylene oxide diol, or combinations thereof; wherein saidchain extender is hydrazine, ethylene diamine, or 2-methylpentamethylenediamine, hexane diamine, or m-xylene diamine, or combinations thereof.8. The polymeric dispersion comprising the polyurethane of claim
 1. 9.The polymeric dispersion comprising the polyurethane of claim
 3. 10. Thepolymeric dispersion comprising the polyurethane of claim
 5. 11. Thepolymeric dispersion comprising the polyurethane of claim
 7. 12. Thepolymeric solution comprising the polyurethane of claim
 1. 13. Thepolymeric solution comprising the polyurethane of claim
 6. 14. The drypolyurethane comprising the composition of claim
 1. 15. A polymericdispersion comprising: an aqueous dispersion of the polyurethane ofclaim 2; wherein said polyurethane comprises: at least one repeat unitderived from said hydroxyl-terminated thiocarbonate containing compoundcomprising block formula AA, or block formula BB, or block formula CC(mono), or block formula CC (di), or block formula EE (mono), or blockformula EE (di), or combinations thereof, including at least one repeatunit derived from said ionic dispersant; and including at least onerepeat unit derived from said chain extender.
 16. A polymeric dispersioncomprising: an aqueous dispersion of the polyurethane of claim 4;wherein said polyurethane comprises: at least one repeat unit derivedfrom said hydroxyl-terminated thiocarbonate containing compoundcomprising block formula AA, or block formula BB, or block formula CC(mono), or block formula CC (di), or block formula EE (mono), or blockformula EE (di), or combinations thereof, including at least one repeatunit derived from said ionic dispersant; and including at least onerepeat unit derived from said chain extender.
 17. A polymeric dispersioncomprising: an aqueous dispersion of the polyurethane of claim 6;wherein said polyurethane comprises: at least one repeat unit derivedfrom said hydroxyl-terminated thiocarbonate containing compoundcomprising block formula AA, or block formula BB, or block formula CC(mono), or block formula CC (di), or block formula EE (mono), or blockformula EE (di), or combinations thereof, including at least one repeatunit derived from said ionic dispersant; and including at least onerepeat unit derived from said chain extender.
 18. A polymeric dispersioncomprising: an aqueous dispersion of the polyurethane of claim 7;wherein said polyurethane comprises: at least one repeat unit derivedfrom said hydroxyl-terminated thiocarbonate containing compoundcomprising block formula AA, or block formula BB, or block formula CC(mono), or block formula CC (di), or block formula EE (mono), or blockformula EE (di), or combinations thereof, including at least one repeatunit derived from said anionic dispersant; including at least one repeatunit derived from said chain extender, and including at least one repeatunit derived from said active hydrogen compound.
 19. A polymericsolution, comprising: a solvent; and the polyurethane of claim 2;wherein said polyurethane comprises: at least one repeat unit derivedfrom said hydroxyl-terminated thiocarbonate containing compoundcomprising block formula AA, or block formula BB, or block formula CC(mono), or block formula CC (di), or block formula EE (mono), or blockformula EE (di), or combinations thereof; and including at least onerepeat unit derived from said chain extender.
 20. The polymericsolution, comprising: a solvent; and the polyurethane of claim 5;wherein said polyurethane comprises: said hydroxyl-terminatedthiocarbonate containing compound comprising block formula AA, or blockformula BB, or block formula CC (mono), or block formula CC (di), orblock formula EE (mono), or block formula EE (di), or combinationsthereof; and including at least one repeat unit derived from said chainextender.
 21. A polymeric dispersion, comprising: an aqueous dispersionof the polyurethane of claim 2; wherein said polyurethane comprises: atleast one repeat unit derived from a hydroxyl-terminated thiocarbonatecontaining compound of formula AA, or formula BB, or formula CC (mono),or formula CC (di), or formula EE (mono), or formula EE (di), orcombinations thereof; including at least one repeat unit derived fromsaid active hydrogen compound; including at least one repeat unitderived from said ionic dispersant; and including at least one repeatunit derived from said chain extender; and subsequently wherein said atleast one thiocarbonate repeat unit is reacted with at least one saidconjugated diene monomer, or at least one said vinyl monomer, orcombinations thereof.
 22. A polymeric dispersion, comprising: an aqueousdispersion of the polyurethane of claim 3; wherein said polyurethanecomprises: at least one repeat unit derived from a hydroxyl-terminatedthiocarbonate containing compound having the formula AA, or formula BB,or formula CC (mono), or formula CC (di), or formula EE (mono), orformula EE (di), or combinations thereof; including at least one repeatunit derived from said active hydrogen compound; including at least onerepeat unit derived from said ionic dispersant; and including at leastone repeat unit derived from said chain extender; and subsequentlywherein said at least one thiocarbonate repeat unit is reacted with atleast one said conjugated diene monomer, or at least one said vinylmonomer, or combinations thereof.
 23. A polymeric dispersion,comprising: an aqueous dispersion of the polyurethane of claim 5;wherein said polyurethane comprises: wherein said polyurethane containsat least one repeat unit derived from a hydroxyl-terminatedthiocarbonate containing compound having the formula formula AA, orformula BB, or formula CC (mono), or formula CC (di), or formula EE(mono), or formula EE (di), or combinations thereof; including at leastone repeat unit derived from said active hydrogen compound; including atleast one repeat unit derived from said ionic dispersant; and includingat least one repeat unit derived from said chain extender; andsubsequently wherein said at least one thiocarbonate repeat unit isreacted with at least one said conjugated diene monomer, or at least onesaid vinyl monomer, or combinations thereof.
 24. A polymeric dispersion,comprising: an aqueous dispersion of the polyurethane of claim 6;wherein said polyurethane comprises: wherein said polyurethane containsat least one repeat unit derived from a hydroxyl-terminatedthiocarbonate containing compound having the formula formula AA, orformula BB, or formula CC (mono), or formula CC (di), or formula EE(mono), or formula EE (di), or combinations thereof; including at leastone repeat unit derived from said active hydrogen compound; including atleast one repeat unit derived from said ionic dispersant; and includingat least one repeat unit derived from said chain extender; andsubsequently wherein said at least one thiocarbonate repeat unit isreacted with at least one said conjugated diene monomer, or at least onesaid vinyl monomer, or combinations thereof.
 25. A polymeric dispersion,comprising: an aqueous dispersion of the polyurethane of claim 7;wherein said polyurethane comprises: wherein said polyurethane containsat least one repeat unit derived from a hydroxyl-terminatedthiocarbonate containing compound having the formula formula AA, orformula BB, or formula CC (mono), or formula CC (di), or formula EE(mono), or formula EE (di), or combinations thereof; including at leastone repeat unit derived from said active hydrogen compound; including atleast one repeat unit derived from said ionic dispersant; and includingat least one repeat unit derived from said chain extender; andsubsequently wherein said at least one thiocarbonate repeat unit isreacted with at least said one conjugated diene monomer, or at least onesaid vinyl monomer, or combinations thereof.
 26. A block copolymerdispersion, comprising: at least one polyurethane block polymercomprising at least one repeat unit derived from a monoisocyanate or apolyisocyanate, at least one repeat unit derived from active hydrogencompound capable of reacting with said isocyanate, and optionally atleast one repeat unit derived from a dispersant; and at least onethiocarbonate block polymer derived from a thiocarbonate compound havingthe formula

wherein, in the above formulas: each R¹ and R², independently, is alinear or branched alkyl having from 1 to about 6 carbon atoms, or asubstituted C₁ to about C₆ alkyl having one or more substituents, or oneor more aryls, or a substituted aryl having from 1 to 6 substituents onthe aryl ring; wherein said one or more substituents, independently,comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or ahalogen which can be the same or different, or a cyano, or an etherhaving a total of from 2 to about 20 carbon atoms, or a nitro, orcombinations thereof; or wherein R¹ and R² are part of a cyclic ringhaving from about 5 to about 12 total carbon atoms; R³ is benzyl, a C₁through C₁₈ alkyl, or a substituted C₁ to C₁₈ alkyl wherein saidsubstituted group is halogen, hydroxyl, or alkoxy, or a C₁ to C₁₈hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl,carboalkoxyalkyl, or mercaptoalkyl, each R⁴ and R⁵, independently, isoptionally substituted, and is a linear or branched alkyl having from 1to about 12 carbon atoms; or an aryl having from 6 to about 18 carbonatoms, optionally containing heteroatoms; or wherein said R⁴ and said R⁵substituents, independently, comprise an alkyl having from 1 to 6 carbonatoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20carbon atoms, a nitro, or combinations thereof, or R⁴ and R⁵ can form asubstituted or unsubstituted cyclic ring having from 3 to about 12carbon atoms; wherein R⁶ and R⁷, independently, is optionallysubstituted and optionally contains heteroatoms; and is hydrogen; alinear or branched alkyl having from 1 to about 18 carbon atoms, an arylhaving from 6 to about 18 carbon atoms optionally saturated orunsaturated; an arylalkyl having from about 7 to about 18 carbon atoms;an alkenealkyl having from 3 to about 18 carbon atoms; or is derivedfrom a polyalkylene glycol ether having from 3 to about 200 carbonatoms; or is derived from piperazine, morpholine, pyrrolidone,piperidine, 4-alkyl amino-2,2,6,6-tetramethyl piperidine,1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine,phenothiazine, iminodibenzyl, phenoxazine,N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivativesthereof; or R⁶ and R⁷ can form a substituted or unsubstituted cyclicring having a total of from 4 to about 12 carbon atoms; and wherein saidsubstituents, independently, are the same as R¹³; R¹³ is optionallysubstituted, and is a linear or branched alkyl or alkylene having from 1to about 12 carbon atoms, an aryl optionally saturated or unsaturated;an arylalkyl having from about 7 to about 18 carbon atoms; an acyl; analkene group; an alkenealkyl having from 3 to about 18 carbon atoms; analkylene group; an alkoxyalkyl derived from a polyalkylene glycol orderived from a polyalkylene glycol monoalkyl ether having from about 3to about 200 carbon atoms or derived from a polyalkylene glycol monoarylether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;a phosphorous containing alkyl; or a substituted or unsubstituted arylring containing heteroatoms; wherein the R³ substituents comprise analkyl having from 1 to 6 carbon atoms; an aryl; a halogen such asfluorine or chlorine; a cyano group; an amino group; an alkene group; analkoxycarbonyl group; an aryloxycarbonyl group; a carboxy group; anacyloxy group; a carbamoyl group; an alkylcarbonyl group; analkylarylcarbonyl group; an arylcarbonyl group; an arylalkylcarbonylgroup; a phthalimido group; a maleimido group; a succinimido group;amidino group; guanidimo group; allyl group; epoxy group; alkoxy group;an alkali metal salt; a quaternary ammonium salt; a hydroxyl group; anether having a total of from 2 to about 20 carbon atoms; a nitro;sulfur; phosphorous; a carboalkoxy group; a heterocyclic groupcontaining one or more sulfur, oxygen or nitrogen atoms, or combinationsthereof; each R¹⁴ is derived from a polyol, wherein said polyolcomprises a substantial hydrocarbon polyol and wherein R¹⁴ comprises analkyl or an alkylene group, or a substituted alkyl or alkylene grouphaving from 2 to about 200 carbon atoms, and wherein said substitutedalkyl or alkylene group comprises oxygen, or a halogen; polyesterpolyol, polyether polyol, polyhydroxy polyester amide, polyolefin,hydroxyl-containing polycaprolactone, hydroxyl-containing acrylicinterpolymer, hydroxyl-containing epoxide, polyhydroxy polycarbonate,polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol,ethoxylated polysiloxane polyol, polybutadiene polyol, hydrogenatedpolybutadiene polyol, polyacrylate polyol, halogenated polyester polyol,or halogenated polyether polyol, or combinations thereof; wherein T is adivalent radical having a nitrogen atom directly attached to a carbonatom of the thiocarbonyl group, and wherein said m and said n,independently, is from about 1 to about 10,000; wherein said conjugateddiene monomer has a total of from 4 to about 12 carbon atoms; whereinsaid vinyl monomer has the formula

where R¹⁵ comprises hydrogen, halogen, C₁ to C₄ alkyl, or substitutedC₁-C₄ alkyl wherein the substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR¹⁷), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc, or an ammonium salt,acyloxy, aroyloxy(O₂CR¹⁷), alkoxy-carbonyl(CO₂R¹⁷), or aryloxy-carbonyl;wherein R¹⁶ comprises hydrogen, R¹⁷, CO₂H, CO₂R¹⁷, COR¹⁷, CN, CONH₂,CONHR¹⁷, O₂CR¹⁷, OR¹⁷, or halogen; R¹⁷, independently, comprises C₁-C₁₈alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl, heterocyclyl,aralkyl, or alkaryl, wherein the substituents independently comprise oneor more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts),sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato,cyano, silyl, halo and dialkylamino; or wherein said vinyl containingmonomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide,N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;styrene, α methyl styrene, C₁,-C₁₂ alkyl styrenes with substitute groupseither on the chain or on the ring, or combinations thereof; and whereinsaid thiocarbonate block copolymer is connected to said mono orpolyisocyanate of said polyurethane block.
 27. The block copolymeraccording to claim 26, wherein said active hydrogen compound comprises ahydrocarbon polyol having a total of from 1 to about 20 carbon atoms, apolyester polyol, a polyether polyol, polyhydroxy polyester amides,hydroxyl-containing polycaprolactone, hydroxyl-containing acrylicinterpolymer, hydroxyl-containing epoxide, polyhydroxy polycarbonate,polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol,ethoxylated polysiloxane polyol, polybutadiene polyol and hydrogenatedpolybutadiene polyol, polyacrylate polyol, halogenated polyester polyolor halogenated polyether polyol, or combinations thereof; including saiddispersant, wherein said dispersant comprises a side-chain containingalkylene oxide monomer wherein said alkylene oxide side chain units havefrom 2 to about 10 carbon atoms and are unsubstituted, substituted, orboth unsubstituted and substituted with at least about 50 wt. % of saidalkylene oxide groups being ethylene oxide; or wherein said dispersantmonomer has the formula (HO)_(x)Q(COOH)_(y), wherein Q is a straight orbranched hydrocarbon radical having 1 to 12 carbon atoms, and wherein xand y are 1 to 3; and wherein T is

wherein R⁸ and R⁹, independently, is optionally substituted and ishydrogen, a linear or branched alkyl having from 1 to about 18 carbonatoms, an aryl group having from about 6 to about 18 carbon atoms, anarylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl havingfrom 3 to about 18 carbon atoms, wherein the substituents can be thesame as described herein for R¹ and R²; wherein R¹⁰ is optionallysubstituted, or is non-existent, or an alkylene group having from 1 toabout 18 carbon atoms with about 1 to about 6 carbon atoms preferred, orderived from a polyalkylene glycol ether having from 3 to about 200carbon atoms, wherein the substituents can be the same as describedherein for R¹ and R² or are hereroatoms such as oxygen, nitrogen, sulfuror phosphorous; and wherein R¹¹ and R¹², independently, is an alkylenegroup having from 1 to 4 carbon atoms, with R¹¹ and R¹² having a totalof from about 3 to about 5 carbon atoms, wherein R¹¹ and R¹²,independently, is optionally substituted and wherein said substitutedare, independently, R¹ and R²; and wherein said isocyanate compoundcomprises an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate,or an aromatic polyisocyanate, or combinations thereof.
 28. The blockcopolymer according to claim 27, wherein said active hydrogen compoundis said hydrocarbon polyol is a diol having from 2 to about 20 carbonatoms, or a polyester polyol derived from an organic polycarboxylic acidor an anhydride thereof having from 1 to about 20 carbon atoms and adiol having from 2 to about 20 carbon atoms, or said polyether polyolhaving from 2 to about 15 carbon atoms in the repeat group, or saidpolycarbonate derived from a diol and a diarylcarbonate, or combinationsthereof; wherein said thiocarbonate containing compound is derived fromsaid block formula BB, or said block formula CC (mono), or said blockformula EE (mono), or combinations thereof; and wherein said dienemonomer is 1,3-butadiene, isoprene, 1,3-pentadiene,2,3-dimethyl-1-3-butadiene, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene, or combinations thereof; and wherein saidvinyl monomer is methyl methacrylate, ethyl methacrylate, propylmethacrylate (all isomers), butyl methacrylate (all isomers),2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid,benzyl methacrylate, phenyl methacrylate, methacrylonitrile,alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate(all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate,isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate,acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethylmethacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutylmethacrylate (all isomers), N,N-dimethylaminoethyl methacrylate,N,N-diethylaminoethyl methacrylate, triethyleneglycol methacrylate;itaconic anhydride, itaconic acid; sodium and zinc salts; itaconic acidand 2-acrylamido-2-methyl-1-propanesulfonic acid; N-vinylimidazole,vinylpyridine N-oxide, 4-vinylpyridine carboxymethylbetaine, diallyldimethylammonium chloride, p-styrenesulfonic acid, p-styrenecarboxylicacid, 2-dimethylaminioethyl acrylate and its alkyl or hydrogen halidesalts, 2-dimethyl-aminoethyl methacrylate and its alkyl or hydrogenhalide salts, N-(3-dimethyl-aminopropyl)acrylamide,N-(3-dimethylaminoproyl)methacrylamide, diacetone acrylamide,2-(acetoacetoxy)ethyl methacrylate, 2-(acryloyloxy)ethyl acetoacetate,3-trialkoxysilylpropylmethacrylate (methoxy, ethoxy, isopropoxy),glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (allisomers), hydroxybutyl acrylate (all isomers), N,N-diethylaminoethylacrylate, triethyleneglycol acrylate, methacrylamide,N-methylacrylamide, N,N-dimethyl-acrylamide, N-tertbutylmethacrylamide,N—N-butylmethacrylamide, N-methylol-methacrylamide,N-ethylolmethacrylamide, N-tertbutylacrylamide, N—N-butyl-acrylamide,N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (allisomers), diethylaminostyrene (all isomers), alpha-methylvinyl benzoicacid (all isomers), diethylamino alpha-methylstyrene (all isomers),p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic sodium salt,trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate,tributoxysilylpropyl methacrylate, dimethoxy-methylsilylpropylmethacrylate, diethoxymethylsilylpropyl methacrylate,dibutoxy-methylsilylpropyl methacrylate, diisopropoxymethylsilylpropylmethacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropylmethacrylate, dibutoxy silylpropyl methacrylate, diisopropoxysilylpropylmethacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropylacrylate, tributoxysilylpropyl acrylate, dimethoxy-methylsilylpropylacrylate, diethoxymethylsilylpropyl acrylate, dibutoxy-methylsilylpropylacrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxy-silylpropylacrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate,diisopropoxysilylpropyl amiate, vinyl acetate, vinyl butyrate, vinylbenzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleicanhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone,N-vinylcarbazole, butadiene, isoprene, chloroprene, ethylene, andpropylene; wherein each said m and n is from about 5 to about 500;wherein, in each said formulation, each R¹ and R², independently, ismethyl, or phenyl; wherein each R³, independently, is an alkyl havingfrom 1 to about 18 carbon atoms; wherein each said R⁴ and R⁵,independently, is methyl or phenyl; wherein each said R⁶ and R⁷,independently, is a phenyl, an alkyl or a substituted alkyl having from1 to about 18 carbon atoms; wherein each said R¹³, independently, is analkyl or an alkylene having from 1 to about 6 carbon atoms; wherein saidaliphatic polyisocyanate has a total of from 5 to about 20 carbon atoms,wherein said cycloaliphatic polyisocyanate contains from about 6 toabout 20 carbon atoms, and wherein aromatic polyisocyanate contains fromabout 8 to about 20 carbon atoms; and wherein said (HO)_(x)Q(COOH)_(y)dispersant comprises citric acid, dimethylol propanoic acid (DMPA),dimethylol butanoic acid (DMBA), glycolic acid, thioglycolic acid,tartaric acid, dihydroxy tartaric acid, lactic acid, maleic acid,dihydroxymalic acid, or combinations thereof.
 29. The block copolymeraccording to claim 28, wherein said conjugated diene monomer isbutadiene, isoprene, or combinations thereof; and wherein said vinylmonomer is C₁-C₁₈ acrylate; acrylic acid; C₁-C₈ monoalkyl and dialkylacrylamide; a combination of C₁-C₈ acrylate and methacrylate; acombination of said acrylamide and C₁-C₈ monoalkyl and dialkylmethacrylamide; wherein said R¹⁴ polyol is said substantiallyhydrocarbon polyol and wherein said alkyl or alkylene group, or saidsubstituted alkyl or alkylene group has from 2 to about 10 carbon atoms;wherein said aliphatic polyisocyanate comprises tetramethylenediisocyanate, hexamethylene-1,6-diisocyanate (HDI), decamethylenediisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylenediisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate,2-methyl-1,5-pentamethylene diisocyanate, or combinations thereof,wherein said cycloaliphatic polyisocyanate comprisescyclobutane-1,3-diisocyanate, 1,2-, 1,3- and 1,4-cyclohexanediisocyanates, 2,4- and 2,6-methylcyclohexane diisocyanate, 4,4′- and2,4′-dicyclohexyldiisocyanates, 1,3,5-cyclohexane triisocyanates,isocyanatomethylcyclohexane isocyanates, isocyanatoethylcyclohexaneisocyanates, bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4′- and2,4′-bis(isocyanatomethyl) dicyclohexane, isophorone diisocyanate,derivatives, dimers, or trimers thereof, or combinations thereof;wherein said aromatic polyisocyanate comprises 2,4- and2,6-hexahydrotoluenediisocyanate, 1,2, 1,3, and 1,4-phenylenediisocyanates, triphenyl methane-4,4′,4″-triisocyanate,naphthylene-1,5-diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI),2,4′-, 4,4′- and 2,2-biphenyl diisocyanates, 2,2′-, 2,4′- and4,4′-diphenylmethane diisocyanates (MDI), polyphenyl polymethylenepolyisocyanates (PMDI), mixtures of MDI and PMDI, mixtures of PMDI andTDI, aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylylenediisocyanates and m-tetramethylxylyene diisocyanate (TMXDI), or modifiedpolyisocyanates thereof including dimers and trimers, or combinationsthereof; wherein said dispersant is trimethylol propane monoethoxylatemethyl ether, DMPA, or DMBA, or combinations thereof; and wherein saidactive hydrogen compound is said hydrocarbon diol, said polyester diol,said polyether diol, or said polycarbonate diol.
 30. The block copolymeraccording to claim 26, wherein said block copolymer is an AB block or an(AB)_(n)A block copolymer where n equals 1 to about 20; and wherein Ablock is said thiocarbonate block and said B block is said polyurethaneblock.
 31. The block copolymer according to claim 28, wherein said blockcopolymer is an AB block or an (AB)_(n)A block copolymer where n equals1 to about 20; and wherein A block is said thiocarbonate block and saidB block is said polyurethane block.
 32. The block copolymer according toclaim 29, wherein said block copolymer is an AB block or an (AB)_(n)Ablock copolymer where n equals 1 to about 20; and wherein A block issaid thiocarbonate block and said B block is said polyurethane block.33. A coating on a substrate, said coating comprising the composition ofclaim 1, and wherein said substrate comprises wood, metal, glass, cloth,leather, paper, plastic, or foam, or any combination thereof.
 34. Acoating on a substrate, said coating comprising the composition of claim4, and wherein said substrate comprises wood, metal, glass, cloth,leather, paper, plastic, or foam, or any combination thereof.
 35. Acoating on a substrate, said coating comprising the composition of claim1, and wherein said substrate is wood.
 36. A coating on a fabric, saidcoating comprising the composition of claim 1, and wherein said fabriccomprises a woven fabric, or a non-woven fabric, or a combinationthereof.
 37. A coating on a fabric, said coating comprising thecomposition of claim 5, and wherein said fabric comprises a wovenfabric, or a non-woven fabric, or a combination thereof.
 38. A personalcare product comprising as a component thereof the composition ofclaim
 1. 39. A personal care product comprising as a component thereofthe composition of claim
 5. 40. A process for forming a polyurethanecomprising the steps of: (a) adding to a reaction vessel an isocyanatecompound, a hydroxyl-terminated thiocarbonate compound, optionally anactive hydrogen compound, and optionally a chain extender; saidhydroxyl-terminated thiocarbonate compound having the formula

wherein, in the above formulas: each R¹ and R², independently, is alinear or branched alkyl having from 1 to about 6 carbon atoms, or asubstituted C₁ to about C₆ alkyl having one or more substituents, or oneor more aryls, or a substituted aryl having from 1 to 6 substituents onthe aryl ring; wherein said one or more substituents, independently,comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or ahalogen which can be the same or different, or a cyano, or an etherhaving a total of from 2 to about 20 carbon atoms, or a nitro, orcombinations thereof; or wherein R¹ and R² are part of a cyclic ringhaving from about 5 to about 12 total carbon atoms; R³ is benzyl, a C₁through C₁₈ alkyl, or a substituted C₁ to C₁₈ alkyl wherein saidsubstituted group is halogen, hydroxyl, or alkoxy, or a C₁ to C₁₈hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl,carboalkoxyalkyl, or mercaptoalkyl, each R⁴ and R⁵, independently, isoptionally substituted, and is a linear or branched alkyl having from 1to about 12 carbon atoms; or an aryl having from 6 to about 18 carbonatoms, optionally containing heteroatoms; or wherein said R⁴ and said R⁵substituents, independently, comprise an alkyl having from 1 to 6 carbonatoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20carbon atoms, a nitro, or combinations thereof, or R⁴ and R⁵ can form asubstituted or unsubstituted cyclic ring having from 3 to about 12carbon atoms; wherein R⁶ and R⁷, independently, is optionallysubstituted and optionally contains heteroatoms; and is hydrogen; alinear or branched alkyl having from 1 to about 18 carbon atoms, an arylhaving from 6 to about 18 carbon atoms optionally saturated orunsaturated; an arylalkyl having from about 7 to about 18 carbon atoms;an alkenealkyl having from 3 to about 18 carbon atoms; or is derivedfrom a polyalkylene glycol ether having from 3 to about 200 carbonatoms; or is derived from piperazine, morpholine, pyrrolidone,piperidine, 4-alkyl amino-2,2,6,6-tetramethyl piperidine,1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine,phenothiazine, iminodibenzyl, phenoxazine,N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivativesthereof; or R⁶ and R⁷ can form a substituted or unsubstituted cyclicring having a total of from 4 to about 12 carbon atoms; and wherein saidsubstituents, independently, are the same as R¹³; R¹³ is optionallysubstituted, and is a linear or branched alkyl or alkylene having from 1to about 12 carbon atoms, an aryl optionally saturated or unsaturated;an arylalkyl having from about 7 to about 18 carbon atoms; an acyl; analkene group; an alkenealkyl having from 3 to about 18 carbon atoms; analkylene group; an alkoxyalkyl derived from a polyalkylene glycol orderived from a polyalkylene glycol monoalkyl ether having from about 3to about 200 carbon atoms or derived from a polyalkylene glycol monoarylether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;a phosphorous containing alkyl; or a substituted or unsubstituted arylring containing heteroatoms; wherein the R¹³ substituents comprise analkyl having from 1 to 6 carbon atoms; an aryl; a halogen such asfluorine or chlorine; a cyano group; an amino group; an alkene group; analkoxycarbonyl group; an aryloxycarbonyl group; a carboxy group; anacyloxy group; a carbamoyl group; an alkylcarbonyl group; analkylarylcarbonyl group; an arylcarbonyl group; an arylalkylcarbonylgroup; a phthalimido group; a maleimido group; a succinimido group;amidino group; guanidimo group; allyl group; epoxy group; alkoxy group;an alkali metal salt; a quaternary ammonium salt; a hydroxyl group; anether having a total of from 2 to about 20 carbon atoms; a nitro;sulfur; phosphorous; a carboalkoxy group; a heterocyclic groupcontaining one or more sulfur, oxygen or nitrogen atoms, or combinationsthereof; each R¹⁴ is derived from a polyol, wherein said polyolcomprises a hydrocarbon polyol and wherein R¹⁴ comprises an alkyl or analkylene group, or a substituted alkyl or alkylene group having from 2to about 200 carbon atoms, and wherein said substituted alkyl oralkylene group comprises oxygen, or a halogen; polyester polyol,polyether polyol, polyhydroxy polyester amide, hydroxyl-containingpolycaprolactone, hydroxyl-containing acrylic interpolymer,hydroxyl-containing epoxide, polyhydroxy polycarbonate, polyhydroxypolyacetal, polyhydroxy polythioether, polysiloxane polyol, ethoxylatedpolysiloxane polyol, polybutadiene polyol, hydrogenated polybutadienepolyol, polyacrylate polyol, halogenated polyester polyol, orhalogenated polyether polyol, or combinations thereof; wherein T is adivalent radical having a nitrogen atom directly attached to a carbonatom of a thiocarbonyl group, and wherein said m and said n,independently, is from about 1 to about 10,000; wherein said conjugateddiene monomer has a total of from 4 to about 12 carbon atoms; whereinsaid vinyl monomer has the formula

where R¹⁵ comprises hydrogen, halogen, C₁ to C₄ alkyl, or substitutedC₁-C₄ alkyl wherein the substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR¹⁷), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc, or an ammonium salt,acyloxy, aroyloxy(O₂CR¹⁷), alkoxy-carbonyl(CO₂R¹⁷), or aryloxy-carbonyl;wherein R¹⁶ comprises hydrogen, R¹⁷, CO₂H, CO₂R¹⁷, COR¹⁷, CN, CONH₂,CONHR¹⁷, O₂CR¹⁷, OR¹⁷, or halogen; R¹⁷, independently, comprises C₁-C₁₈alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl, heterocyclyl,aralkyl, or alkaryl, wherein the substituents independently comprise oneor more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts),sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato,cyano, silyl, halo and dialkylamino; or wherein said vinyl containingmonomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide,N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;styrene, α methyl styrene, C₁,-C₁₂ alkyl styrenes with substitute groupseither on the chain or on the ring, or combinations thereof; andreacting said compounds to form a thermoplastic polyurethane.
 41. Aprocess according to claim 40, wherein said active hydrogen compoundcomprises a hydrocarbon polyol having a total of from 1 to about 10carbon atoms, a polyester polyol, a polyether polyol, polyhydroxypolyester amides, hydroxyl-containing polycaprolactone,hydroxyl-containing acrylic interpolymer, hydroxyl-containing epoxide,polyhydroxy polycarbonate, polyhydroxy polyacetal, polyhydroxypolythioether, polysiloxane polyol, ethoxylated polysiloxane polyol,polybutadiene polyol and hydrogenated polybutadiene polyol, polyacrylatepolyol, halogenated polyester polyol or halogenated polyether polyol, orcombinations thereof; wherein T is

wherein R⁸ and R⁹, independently, is optionally substituted and ishydrogen, a linear or branched alkyl having from 1 to about 18 carbonatoms, an aryl group having from about 6 to about 18 carbon atoms, anarylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl havingfrom 3 to about 18 carbon atoms, wherein the substituents can be thesame as described herein for R¹ and R²; wherein R¹⁰ is optionallysubstituted, or is non-existent, or an alkylene group having from 1 toabout 18 carbon atoms with about 1 to about 6 carbon atoms preferred, orderived from a polyalkylene glycol ether having from 3 to about 200carbon atoms, wherein the substituents can be the same as describedherein for R¹ and R² or are hereroatoms such as oxygen, nitrogen, sulfuror phosphorous; and wherein R¹¹ and R¹², independently, is an alkylenegroup having from 1 to 4 carbon atoms, with R¹¹ and R¹² having a totalof from about 3 to about 5 carbon atoms, wherein R¹¹ and R¹²,independently, is optionally substituted and wherein said substitutedare, independently, R¹ and R²; and wherein said isocyanate compoundcomprises an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate,or an aromatic polyisocyanate, or combinations thereof.
 42. A processaccording to claim 41, wherein said thiocarbonate is said Block FormulaAA, or said Block Formula BB, or said Block Formula CC (mono), or saidBlock Formula CC (di), or said Block Formula EE (mono), or said BlockFormula EE (di); wherein said active hydrogen compound is saidhydrocarbon polyol is a diol having from 2 to about 20 carbon atoms, ora polyester polyol derived from an organic polycarboxylic acid or ananhydride thereof having from 1 to about 20 carbon atoms and a diolhaving from 2 to about 20 carbon atoms, or said polyether polyol havingfrom 2 to about 15 carbon atoms in the repeat group, or saidpolycarbonate derived from a diol and a diarylcarbonate, or combinationsthereof; wherein said diene monomer is 1,3-butadiene, isoprene,1,3-pentadiene, 2,3-dimethyl-1-3-butadiene, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene, or combinations thereof; and wherein saidvinyl monomer is methyl methacrylate, ethyl methacrylate, propylmethacrylate (all isomers), butyl methacrylate (all isomers),2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid,benzyl methacrylate, phenyl methacrylate, methacrylonitrile,alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate(all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate,isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate,acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethylmethacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutylmethacrylate (all isomers), N,N-dimethylaminoethyl methacrylate,N,N-diethylaminoethyl methacrylate, triethyleneglycol methacrylate;itaconic anhydride, itaconic acid; sodium and zinc salts; itaconic acidand 2-acrylamido-2-methyl-1-propanesulfonic acid; N-vinylimidazole,vinylpyridine N-oxide, 4-vinylpyridine carboxymethylbetaine, diallyldimethylammonium chloride, p-styrenesulfonic acid, p-styrenecarboxylicacid, 2-dimethylaminioethyl acrylate and its alkyl or hydrogen halidesalts, 2-dimethyl-aminoethyl methacrylate and its alkyl or hydrogenhalide salts, N-(3-dimethyl-aminopropyl)acrylamide,N-(3-dimethylaminoproyl)methacrylamide, diacetone acrylamide,2-(acetoacetoxy)ethyl methacrylate, 2-(acryloyloxy)ethyl acetoacetate,3-trialkoxysilylpropylmethacrylate (methoxy, ethoxy, isopropoxy),glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (allisomers), hydroxybutyl acrylate (all isomers), N,N-diethylaminoethylacrylate, triethyleneglycol acrylate, methacrylamide,N-methylacrylamide, N,N-dimethyl-acrylamide, N-tertbutylmethacrylamide,N—N-butylmethacrylamide, N-methylol-methacrylamide,N-ethylolmethacrylamide, N-tertbutylacrylamide, N—N-butyl-acrylamide,N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (allisomers), diethylaminostyrene (all isomers), alpha-methylvinyl benzoicacid (all isomers), diethylamino alpha-methylstyrene (all isomers),p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic sodium salt,trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate,tributoxysilylpropyl methacrylate, dimethoxy-methylsilylpropylmethacrylate, diethoxymethylsilylpropyl methacrylate,dibutoxy-methylsilylpropyl methacrylate, diisopropoxymethylsilylpropylmethacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropylmethacrylate, dibutoxy silylpropyl methacrylate, diisopropoxysilylpropylmethacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropylacrylate, tributoxysilylpropyl acrylate, dimethoxy-methylsilylpropylacrylate, diethoxymethylsilylpropyl acrylate, dibutoxy-methylsilylpropylacrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxy-silylpropylacrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate,diisopropoxysilylpropyl amiate, vinyl acetate, vinyl butyrate, vinylbenzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleicanhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone,N-vinylcarbazole, butadiene, isoprene, chloroprene, ethylene, andpropylene; wherein each said m and n is from about 5 to about 500;wherein, in each said formulation, each R¹ and R², independently, ismethyl, or phenyl; wherein each R³, independently, is an alkyl havingfrom 1 to about 18 carbon atoms; wherein each said R⁴ and R⁵,independently, is methyl or phenyl; wherein each said R⁶ and R⁷,independently, is a phenyl, an alkyl or a substituted alkyl having from1 to about 18 carbon atoms; wherein each said R¹³, independently, is analkyl or an alkylene having from 1 to about 6 carbon atoms; wherein saidaliphatic polyisocyanate has a total of from 5 to about 20 carbon atoms,wherein said cycloaliphatic polyisocyanate contains from about 6 toabout 20 carbon atoms, and wherein aromatic polyisocyanate contains fromabout 8 to about 20 carbon atoms.
 43. A process according to claim 42,including said active hydrogen compound, including said chain extender,and including carrying out said reaction in an extruder; wherein saidconjugated diene monomer is butadiene, isoprene, or combinationsthereof; and wherein said vinyl monomer is C₁-C₁₈ acrylate; acrylicacid; C₁-C₈ monoalkyl and dialkyl acrylamide; a combination of C₁-C₈acrylate and methacrylate; a combination of said acrylamide and C₁-C₈monoalkyl and dialkyl methacrylamide; wherein said R¹⁴ polyol is saidsubstantially hydrocarbon polyol and wherein said alkyl or alkylenegroup, or said substituted alkyl or alkylene group has from 2 to about10 carbon atoms; wherein said aliphatic polyisocyanate comprisestetramethylene diisocyanate, hexamethylene-1,6-diisocyanate (HDI),decamethylene diisocyanate, 1,12-dodecane diisocyanate,2,2,4-trimethyl-hexamethylene diisocyanate,2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, or combinations thereof, wherein said cycloaliphaticpolyisocyanate comprises cyclobutane-1,3-diisocyanate, 1,2-, 1,3- and1,4-cyclohexane diisocyanates, 2,4- and 2,6-methylcyclohexanediisocyanate, 4,4′- and 2,4′-dicyclohexyldiisocyanates,1,3,5-cyclohexane triisocyanates, isocyanatomethylcyclohexaneisocyanates, isocyanatoethylcyclohexane isocyanates,bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4′- and2,4′-bis(isocyanatomethyl) dicyclohexane, isophorone diisocyanate,derivatives, dimers, or trimers thereof, or combinations thereof;wherein said aromatic polyisocyanate comprises 2,4- and2,6-hexahydrotoluenediisocyanate, 1,2, 1,3, and 1,4-phenylenediisocyanates, triphenyl methane-4,4′,4″-triisocyanate,naphthylene-1,5-diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI),2,4′-, 4,4′- and 2,2-biphenyl diisocyanates, 2,2′-, 2,4′- and4,4′-diphenylmethane diisocyanates (MDI), polyphenyl polymethylenepolyisocyanates (PMDI), mixtures of MDI and PMDI, mixtures of PMDI andTDI, aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylylenediisocyanates and m-tetramethylxylyene diisocyanate (TMXDI), or modifiedpolyisocyanates thereof including dimers and trimers, or combinationsthereof; and wherein said active hydrogen compound is said hydrocarbondiol, said polyester diol, said polyether diol, or said polycarbonatediol.
 44. A process according to claim 40, wherein said reaction vesselis an extruder, and polymerizing said components in said extruder.
 45. Aprocess according to claim 43, wherein said reaction vessel is anextruder, and polymerizing said components in said extruder.
 46. Aprocess for forming a polyurethane dispersion comprising the steps of:(a) reacting an isocyanate compound, a dispersant, and ahydroxyl-terminated thiocarbonate compound containing repeat groupstherein derived from at least one conjugated diene, or at least onevinyl monomer, or combinations thereof, and forming a polyurethane, saidthiocarbonate compound having the following formula:

optionally an active hydrogen compound and optionally a chain extender;(b) neutralizing said polyurethane and forming a polyurethane dispersionin water; wherein in the above formulas: each R¹ and R², independently,is a linear or branched alkyl having from 1 to about 6 carbon atoms, ora substituted C₁ to about C₆ alkyl having one or more substituents, orone or more aryls, or a substituted aryl having from 1 to 6 substituentson the aryl ring; wherein said one or more substituents, independently,comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or ahalogen which can be the same or different, or a cyano, or an etherhaving a total of from 2 to about 20 carbon atoms, or a nitro, orcombinations thereof; or wherein R¹ and R² are part of a cyclic ringhaving from about 5 to about 12 total carbon atoms; R³ is benzyl, a C₁through C₁₈ alkyl, or a substituted C₁ to C₁₈ alkyl wherein saidsubstituted group is halogen, hydroxyl, or alkoxy, or a C₁ to C₁₈hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl,carboalkoxyalkyl, or mercaptoalkyl, each R⁴ and R⁵, independently, isoptionally substituted, and is a linear or branched alkyl having from 1to about 12 carbon atoms; or an aryl having from 6 to about 18 carbonatoms, optionally containing heteroatoms; or wherein said R⁴ and said R⁵substituents, independently, comprise an alkyl having from 1 to 6 carbonatoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20carbon atoms, a nitro, or combinations thereof, or R⁴ and R⁵ can form asubstituted or unsubstituted cyclic ring having from 3 to about 12carbon atoms; wherein R⁶ and R⁷, independently, is optionallysubstituted and optionally contains heteroatoms; and is hydrogen; alinear or branched alkyl having from 1 to about 18 carbon atoms, an arylhaving from 6 to about 18 carbon atoms optionally saturated orunsaturated; an arylalkyl having from about 7 to about 18 carbon atoms;an alkenealkyl having from 3 to about 18 carbon atoms; or is derivedfrom a polyalkylene glycol ether having from 3 to about 200 carbonatoms; or is derived from piperazine, morpholine, pyrrolidone,piperidine, 4-alkyl amino-2,2,6,6-tetramethyl piperidine,1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine,phenothiazine, iminodibenzyl, phenoxazine,N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivativesthereof; or R⁶ and R⁷ can form a substituted or unsubstituted cyclicring having a total of from 4 to about 12 carbon atoms; and wherein saidsubstituents, independently, are the same as R¹³; R¹³ is optionallysubstituted, and is a linear or branched alkyl or alkylene having from 1to about 12 carbon atoms, an aryl optionally saturated or unsaturated;an arylalkyl having from about 7 to about 18 carbon atoms; an acyl; analkene group; an alkenealkyl having from 3 to about 18 carbon atoms; analkylene group; an alkoxyalkyl derived from a polyalkylene glycol orderived from a polyalkylene glycol monoalkyl ether having from about 3to about 200 carbon atoms or derived from a polyalkylene glycol monoarylether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;a phosphorous containing alkyl; or a substituted or unsubstituted arylring containing heteroatoms; or wherein the R¹³ substituents comprise analkyl having from 1 to 6 carbon atoms; an aryl; a halogen such asfluorine or chlorine; a cyano group; an amino group; an alkene group; analkoxycarbonyl group; an aryloxycarbonyl group; a carboxy group; anacyloxy group; a carbamoyl group; an alkylcarbonyl group; analkylarylcarbonyl group; an arylcarbonyl group; an arylalkylcarbonylgroup; a phthalimido group; a maleimido group; a succinimido group;amidino group; guanidimo group; allyl group; epoxy group; alkoxy group;an alkali metal salt; a quaternary ammonium salt; a hydroxyl group; anether having a total of from 2 to about 20 carbon atoms; a nitro;sulfur; phosphorous; a carboalkoxy group; a heterocyclic groupcontaining one or more sulfur, oxygen or nitrogen atoms, or combinationsthereof; each R¹⁴ is derived from a polyol, wherein said polyolcomprises a hydrocarbon polyol and wherein R¹⁴ comprises an alkyl or analkylene group, or a substituted alkyl or alkylene group having from 2to about 200 carbon atoms, and wherein said substituted alkyl oralkylene group comprises oxygen, or a halogen; polyester polyol,polyether polyol, polyhydroxy polyester amide, hydroxyl-containingpolycaprolactone, hydroxyl-containing acrylic interpolymer,hydroxyl-containing epoxide, polyhydroxy polycarbonate, polyhydroxypolyacetal, polyhydroxy polythioether, polysiloxane polyol, ethoxylatedpolysiloxane polyol, polybutadiene polyol, hydrogenated polybutadienepolyol, polyacrylate polyol, halogenated polyester polyol, orhalogenated polyether polyol, or combinations thereof; wherein T is adivalent radical having a nitrogen atom directly attached to a carbonatom of the thiocarbonyl group; and wherein said m and said n,independently, is from about 1 to about 10,000; wherein said conjugateddiene monomer has from 4 to about 12 carbon atoms; wherein said vinylmonomer has the formula

where R¹⁵ comprises hydrogen, halogen, C₁ to C₄ alkyl, or substitutedC₁-C₄ alkyl wherein the substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR¹⁷), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc, or an ammonium salt,acyloxy, aroyloxy(O₂CR¹⁷), alkoxy-carbonyl(CO₂R¹⁷), or aryloxy-carbonyl;wherein R¹⁶ comprises hydrogen, R¹⁷, CO₂H, CO₂R¹⁷, COR¹⁷, CN, CONH₂,CONHR¹⁷, O₂CR¹⁷, OR¹⁷, or halogen; R¹⁷, independently, comprises C₁-C₁₈alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl, heterocyclyl,aralkyl, or alkaryl, wherein the substituents independently comprise oneor more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts),sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato,cyano, silyl, halo and dialkylamino; or wherein said vinyl containingmonomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide,N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;styrene, cc methyl styrene, C₁,-C₁₂ alkyl styrenes with substitutegroups both either on the chain or on the ring, or combinations thereof.47. The process according to claim 46, wherein said isocyanate compoundcomprises an aliphatic, a cycloaliphatic, or an aromatic polyisocyanate,or combinations thereof; and wherein said dispersant is an ionicdispersant; and wherein optional active hydrogen compound comprises ahydrocarbon polyol having a total of from 1 to about 20 carbon atoms, apolyester polyol, a polyether polyol, polyhydroxy polyester amide,hydroxyl-containing polycaprolactone, hydroxyl-containing acrylicinterpolymer, hydroxyl-containing epoxide, polyhydroxy polycarbonate,polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol,ethoxylated polysiloxane polyol, polybutadiene polyol and hydrogenatedpolybutadiene polyol, polyacrylate polyol, halogenated polyester polyolor halogenated polyether polyol, or combinations thereof.
 48. Theprocess according to claim 47, including neutralizing said dispersantand subsequently adding said polyurethane to water to form saiddispersion; wherein said aliphatic polyisocyanate comprisestetramethylene diisocyanate, hexamethylene-1,6-diisocyanate (HDI),decamethylene diisocyanate, 1,12-dodecane diisocyanate,2,2,4-trimethyl-hexamethylene diisocyanate,2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, or combinations thereof, wherein said cycloaliphaticpolyisocyanate comprises cyclobutane-1,3-diisocyanate, 1,2-, 1,3- and1,4-cyclohexane diisocyanates, 2,4- and 2,6-methylcyclohexanediisocyanate, 4,4′- and 2,4′-dicyclohexyldiisocyanates,1,3,5-cyclohexane triisocyanates, isocyanatomethylcyclohexaneisocyanates, isocyanatoethylcyclohexane isocyanates,bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4′- and2,4′-bis(isocyanatomethyl) dicyclohexane, isophorone diisocyanate,derivatives, dimers, or trimers thereof, or combinations thereof;wherein said aromatic polyisocyanate comprises 2,4- and2,6-hexahydrotoluenediisocyanate, 1,2, 1,3, and 1,4-phenylenediisocyanates, triphenyl methane-4,4′,4″-triisocyanate,naphthylene-1,5-diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI),2,4′-, 4,4′- and 2,2-biphenyl diisocyanates, 2,2′-, 2,4′- and4,4′-diphenylmethane diisocyanates (MDI), polyphenyl polymethylenepolyisocyanates (PMDI), mixtures of MDI and PMDI, mixtures of PMDI andTDI, aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylylenediisocyanates and m-tetramethylxylyene diisocyanate (TMXDI), or modifiedpolyisocyanates thereof including dimers and trimers, or combinationsthereof; wherein said ionic dispersant has the formula(HO)_(x)Q(COOH)_(y), wherein Q is a straight or branched hydrocarbonradical having 1 to 12 carbon atoms, and wherein x and y are 1 to 3;wherein T is

wherein R⁸ and R⁹, independently, is optionally substituted and ishydrogen, a linear or branched alkyl having from 1 to about 18 carbonatoms, an aryl group having from about 6 to about 18 carbon atoms, anarylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl havingfrom 3 to about 18 carbon atoms, wherein the substituents can be thesame as described herein for R¹ and R² wherein R¹⁰ is optionallysubstituted, or is non-existent, or an alkylene group having from 1 toabout 18 carbon atoms with about 1 to about 6 carbon atoms preferred, orderived from a polyalkylene glycol ether having from 3 to about 200carbon atoms, wherein the substituents can be the same as describedherein for R¹ and R² or are hereroatoms such as oxygen, nitrogen, sulfuror phosphorous; and wherein R¹¹ and R¹², independently, is an alkylenegroup having from 1 to 4 carbon atoms, and wherein R¹¹ and R¹²,independently, is optionally substituted and wherein said substituentsare, independently, the same as for R¹ and R²; wherein said activehydrogen compound comprises said hydrocarbon polyol which is a diolhaving from 2 to about 20 carbon atoms or said polyester polyol derivedfrom an organic polycarboxylic acid or an anhydride thereof having from1 to about 20 carbon atoms and a diol having from 2 to about 20 carbonatoms, or said polyether polyol having from 2 to about 15 carbon atoms,or said polycarbonate which is derived from a diol and adiarylcarbonate; and wherein said chain extender is an amine containingchain extender or an organic diol chain extender.
 49. The processaccording to claim 48, including chain extending said polyurethane;wherein said ionic dispersant comprises citric acid, dimethylolpropanoic acid (DMPA), dimethylol butanoic acid (DMBA), glycolic acid,thioglycolic acid, tartaric acid, dihydroxy tartaric acid, lactic acid,maleic acid, dihydroxymalic acid, or combinations thereof; wherein eachsaid m and n is from about 5 to about 500; wherein, in each formulation,each R¹ and R², independently, is methyl, or phenyl; wherein each saidR³, independently, is an alkyl having from 1 to about 18 carbon atoms;wherein each said R⁴ and R⁵, independently, is methyl or phenyl; whereineach said R⁶ and R⁷, independently, is a phenyl, an alkyl or asubstituted alkyl having from 1 to about 18 carbon atoms; wherein eachsaid R³, independently, is an alkyl or an alkylene having from 1 toabout 6 carbon atoms; wherein said R¹⁴ polyol is said substantiallyhydrocarbon polyol and wherein said alkyl or alkylene group, or saidsubstituted alkyl or alkylene group has from 2 to about 10 carbon atoms;wherein said conjugated diene monomer is butadiene, isoprene, orcombinations thereof; and wherein said vinyl monomer is a C₁-C₁₈acrylate; acrylic acid; C₁-C₈ monoalkyl and dialkyl acrylamide; acombination of C₁-C₈ acrylate and methacrylate; a combination of saidacrylamide and C₁-C₈ monoalkyl and dialkyl methacrylamide.
 50. Theprocess according to claim 49, including said active hydrogen compound,and optionally crosslinking said polyurethane.
 51. A process for forminga polyurethane dispersion comprising the steps of: (a) reacting anisocyanate; a dispersant; and a hydroxyl-terminated thiocarbonatecompound; and optionally an active hydrogen compound; and forming apolyurethane in the presence of at least one diluent monomer, saiddiluent monomer comprising at least conjugated diene, or at least onevinyl monomer, or combinations thereof; wherein said thiocarbonatecompound has the formula

(b) neutralizing said polyurethane and forming a dispersion in water;and reacting said conjugated diene or vinyl monomer into saidthiocarbonate compound; wherein in the above formulas: each R¹ and R²,independently, is a linear or branched alkyl having from 1 to about 6carbon atoms, or a substituted C₁ to about C₆ alkyl having one or moresubstituents, or one or more aryls, or a substituted aryl having from 1to 6 substituents on the aryl ring; wherein said one or moresubstituents, independently, comprise an alkyl having from 1 to 6 carbonatoms, or an aryl, or a halogen which can be the same or different, or acyano, or an ether having a total of from 2 to about 20 carbon atoms, ora nitro, or combinations thereof; or wherein R¹ and R² are part of acyclic ring having from about 5 to about 12 total carbon atoms; R³ isbenzyl, a C₁ through C₁₈ alkyl, or a substituted C₁ to C₁₈ alkyl whereinsaid substituted group is halogen, hydroxyl, or alkoxy, or a C₁ to C₁₈hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl,carboalkoxyalkyl, or mercaptoalkyl, each R⁴ and R⁵, independently, isoptionally substituted, and is a linear or branched alkyl having from 1to about 12 carbon atoms; or an aryl having from 6 to about 18 carbonatoms, optionally containing heteroatoms; or wherein said R⁴ and said R⁵substituents, independently, comprise an alkyl having from 1 to 6 carbonatoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20carbon atoms, a nitro, or combinations thereof, or R⁴ and R⁵ can form asubstituted or unsubstituted cyclic ring having from 3 to about 12carbon atoms; and T is a divalent radical having a nitrogen atomdirectly connected to a thiocarbonyl groups; wherein R⁶ and R⁷,independently, is optionally substituted and optionally containsheteroatoms; and is hydrogen; a linear or branched alkyl having from 1to about 18 carbon atoms, an aryl having from 6 to about 18 carbon atomsoptionally saturated or unsaturated; an arylalkyl having from about 7 toabout 18 carbon atoms; an alkenealkyl having from 3 to about 18 carbonatoms; or is derived from a polyalkylene glycol ether having from 3 toabout 200 carbon atoms; or is derived from piperazine, morpholine,pyrrolidone, piperidine, 4-alkyl amino-2,2,6,6-tetramethyl piperidine,1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine,phenothiazine, iminodibenzyl, phenoxazine,N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivativesthereof; or R⁶ and R⁷ can form a substituted or unsubstituted cyclicring having a total of from 4 to about 12 carbon atoms; and wherein saidsubstituents, independently, are the same as R¹³; R¹³ is optionallysubstituted, and is a linear or branched alkyl or alkylene having from 1to about 12 carbon atoms, an aryl optionally saturated or unsaturated;an arylalkyl having from about 7 to about 18 carbon atoms; an acyl; analkene group; an alkenealkyl having from 3 to about 18 carbon atoms; analkylene group; an alkoxyalkyl derived from a polyalkylene glycol orderived from a polyalkylene glycol monoalkyl ether having from about 3to about 200 carbon atoms or derived from a polyalkylene glycol monoarylether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;a phosphorous containing alkyl; or a substituted or unsubstituted arylring containing heteroatoms; wherein the R¹³ substituents comprise analkyl having from 1 to 6 carbon atoms; an aryl; a halogen such asfluorine or chlorine; a cyano group; an amino group; an alkene group; analkoxycarbonyl group; an aryloxycarbonyl group; a carboxy group; anacyloxy group; a carbamoyl group; an alkylcarbonyl group; analkylarylcarbonyl group; an arylcarbonyl group; an arylalkylcarbonylgroup; a phthalimido group; a maleimido group; a succinimido group;amidino group; guanidimo group; allyl group; epoxy group; alkoxy group;an alkali metal salt; a quaternary ammonium salt; a hydroxyl group; anether having a total of from 2 to about 20 carbon atoms; a nitro;sulfur; phosphorous; a carboalkoxy group; a heterocyclic groupcontaining one or more sulfur, oxygen or nitrogen atoms, or combinationsthereof; each R¹⁴ is derived from a polyol, wherein said polyolcomprises a hydrocarbon polyol and wherein R¹⁴ comprises an alkyl or analkylene group, or a substituted alkyl or alkylene group having from 2to about 200 carbon atoms, and wherein said substituted alkyl oralkylene group comprises oxygen, or a halogen; polyester polyol,polyether polyol, polyhydroxy polyester amide, hydroxyl-containingpolycaprolactone, hydroxyl-containing acrylic interpolymer,hydroxyl-containing epoxide, polyhydroxy polycarbonate, polyhydroxypolyacetal, polyhydroxy polythioether, polysiloxane polyol, ethoxylatedpolysiloxane polyol, polybutadiene polyol, hydrogenated polybutadienepolyol, polyacrylate polyol, halogenated polyester polyol, orhalogenated polyether polyol, or combinations thereof; wherein T is adivalent radical having a nitrogen atom directly attached to a carbonatom of a thiocarbonyl group; and wherein said m and said n,independently, is from about 1 to about 10,000; wherein said conjugateddiene monomer has from 4 to about 12 carbon atoms; wherein said vinylmonomer has the formula

where R¹⁵ comprises hydrogen, halogen, C₁ to C₄ alkyl, or substitutedC₁-C₄ alkyl wherein the substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR¹⁷), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc, or an ammonium salt,acyloxy, aroyloxy(O₂CR¹⁷), alkoxy-carbonyl(CO₂R¹⁷), or aryloxy-carbonyl;wherein R¹⁶ comprises hydrogen, R¹⁷, CO₂H, CO₂R¹⁷, COR¹⁷, CN, CONH₂,CONHR¹⁷, O₂CR¹⁷, OR¹⁷, or halogen; R¹⁷, independently, comprises C₁-C₁₈alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl, heterocyclyl,aralkyl, or alkaryl, wherein the substituents independently comprise oneor more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts),sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato,cyano, silyl, halo and dialkylamino; or wherein said vinyl containingmonomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide,N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;styrene, α methyl styrene, C₁,-C₁₂ alkyl styrenes with substitute groupsboth either on the chain or on the ring, or combinations thereof. 52.The process according to claim 51, wherein said dispersant is an ionicdispersant; and wherein optional active hydrogen compound comprises ahydrocarbon polyol having a total of from 1 to about 10 carbon atoms, apolyester polyol, a polyether polyol, polyhydroxy polyester amide,hydroxyl-containing polycaprolactone, hydroxyl-containing acrylicinterpolymer, hydroxyl-containing epoxide, polyhydroxy polycarbonate,polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol,ethoxylated polysiloxane polyol, polybutadiene polyol and hydrogenatedpolybutadiene polyol, polyacrylate polyol, halogenated polyester polyolor halogenated polyether polyol, or combinations thereof.
 53. Theprocess according to claim 52, including neutralizing said dispersantand subsequently adding said polyurethane to water to form saiddispersion, chain extending said polyurethane; and reacting saidconjugated diene or said vinyl monomer or both after said chainextension; wherein said aliphatic polyisocyanate comprisestetramethylene diisocyanate, hexamethylene-1,6-diisocyanate (HDI),decamethylene diisocyanate, 1,12-dodecane diisocyanate,2,2,4-trimethyl-hexamethylene diisocyanate,2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, or combinations thereof, wherein said cycloaliphaticpolyisocyanate comprises cyclobutane-1,3-diisocyanate, 1,2-, 1,3- and1,4-cyclohexane diisocyanates, 2,4- and 2,6-methylcyclohexanediisocyanate, 4,4′- and 2,4′-dicyclohexyldiisocyanates,1,3,5-cyclohexane triisocyanates, isocyanatomethylcyclohexaneisocyanates, isocyanatoethylcyclohexane isocyanates,bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4′- and2,4′-bis(isocyanatomethyl) dicyclohexane, isophorone diisocyanate,derivatives, dimers, or trimers thereof, or combinations thereof;wherein said aromatic polyisocyanate comprises 2,4- and2,6-hexahydrotoluenediisocyanate, 1,2, 1,3, and 1,4-phenylenediisocyanates, triphenyl methane-4,4′,4″-triisocyanate,naphthylene-1,5-diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI),2,4′-, 4,4′- and 2,2-biphenyl diisocyanates, 2,2′-, 2,4′- and4,4′-diphenylmethane diisocyanates (MDI), polyphenyl polymethylenepolyisocyanates (PMDI), mixtures of MDI and PMDI, mixtures of PMDI andTDI, aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylylenediisocyanates and m-tetramethylxylyene diisocyanate (TMXDI), or modifiedpolyisocyanates thereof including dimers and trimers, or combinationsthereof; wherein said ionic dispersant has the formula(HO)_(x)Q(COOH)_(y), wherein Q is a straight or branched hydrocarbonradical having 1 to 12 carbon atoms, and wherein x and y are 1 to 3;wherein T is

wherein R⁸ and R⁹, independently, is optionally substituted and ishydrogen, a linear or branched alkyl having from 1 to about 18 carbonatoms, an aryl group having from about 6 to about 18 carbon atoms, anarylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl havingfrom 3 to about 18 carbon atoms, wherein the substituents can be thesame as described herein for R¹ and R²; wherein R¹⁰ is optionallysubstituted, or is non-existent, or an alkylene group having from 1 toabout 18 carbon atoms with about 1 to about 6 carbon atoms preferred, orderived from a polyalkylene glycol ether having from 3 to about 200carbon atoms, wherein the substituents can be the same as describedherein for R¹ and R² or are hereroatoms such as oxygen, nitrogen, sulfuror phosphorous; and wherein R¹¹ and R¹², independently, is an alkylenegroup having from 1 to 4 carbon atoms, and wherein R¹¹ and R¹²,independently, is optionally substituted and wherein said substituentsare, independently, the same as for R¹ and R²; wherein said activehydrogen compound comprises said hydrocarbon polyol which is a diolhaving from 2 to about 20 carbon atoms or said polyester polyol derivedfrom an organic polycarboxylic acid or an anhydride thereof having from1 to about 20 carbon atoms and a diol having from 2 to about 20 carbonatoms, or said polyether polyol having from 2 to about 15 carbon atoms,or said polycarbonate which is derived from a diol and adiarylcarbonate; and wherein said chain extender is an amine containingchain extender or an organic diol chain extender.
 54. The processaccording to claim 53, including said optional active hydrogen compound;wherein said ionic dispersant comprises citric acid, dimethylolpropanoic acid (DMPA), dimethylol butanoic acid (DMBA), glycolic acid,thioglycolic acid, tartaric acid, dihydroxy tartaric acid, lactic acid,malic acid, dihydroxymalic acid, or combinations thereof; wherein eachsaid m and n is from about 5 to about 500; wherein, in each formulation,each R¹ and R², independently, is methyl, or phenyl; wherein each saidR³, independently, is an alkyl having from 1 to about 18 carbon atoms;wherein each said R⁴ and R⁵, independently, is methyl or phenyl; whereineach said R⁶ and R⁷, independently, is a phenyl, an alkyl or asubstituted alkyl having from 1 to about 18 carbon atoms; wherein eachsaid R¹³, independently, is an alkyl or an alkylene having from 1 toabout 6 carbon atoms; wherein said R¹⁴ polyol is said hydrocarbon polyoland wherein said alkyl or alkylene group, or said substituted alkyl oralkylene group has from 2 to about 10 carbon atoms; wherein saidconjugated diene monomer is butadiene, isoprene, or combinationsthereof; and wherein said vinyl monomers is a C₁-C₁₈ acrylate; acrylicacid; C₁-C₈ monoalkyl and dialkyl acrylamide; a combination of C₁-C₈acrylate and methacrylate; a combination of said acrylamide and C₁-C₈monoalkyl and dialkyl methacrylamide.
 55. The process according to claim54, wherein said isocyanate is a cycloaliphatic isocyanate; andoptionally crosslinking said polyurethane.
 56. A process for forming aneutralized block copolymer dispersion, comprising the steps of:reacting at least one polyurethane block polymer with at least onethiocarbonate block polymer, said polyurethane block comprising at leastone repeat unit derived from an mono-isocyanate or a polyisocyanate, atleast one repeat unit derived from an active hydrogen compound, and atleast one repeat unit derived from a dispersant; said at least onethiocarbonate block copolymer containing repeat units derived from ahydroxyl terminated thiocarbonate containing compound, having theformula

wherein, in the above formulas: each R¹ and R², independently, is alinear or branched alkyl having from 1 to about 6 carbon atoms, or asubstituted C₁ to about C₆ alkyl having one or more substituents, or oneor more aryls, or a substituted aryl having from 1 to 6 substituents onthe aryl ring; wherein said one or more substituents, independently,comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or ahalogen which can be the same or different, or a cyano, or an etherhaving a total of from 2 to about 20 carbon atoms, or a nitro, orcombinations thereof; or wherein R¹ and R² are part of a cyclic ringhaving from about 5 to about 12 total carbon atoms; R³ is benzyl, a C₁through C₁₈ alkyl, or a substituted C₁ to C₁₈ alkyl wherein saidsubstituted group is halogen, hydroxyl, or alkoxy, or a C₁ to C₁₈hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl,carboalkoxyalkyl, or mercaptoalkyl, each R⁴ and R⁵, independently, isoptionally substituted, and is a linear or branched alkyl having from 1to about 12 carbon atoms; or an aryl having from 6 to about 18 carbonatoms, optionally containing heteroatoms; or wherein said R⁴ and said R⁵substituents, independently, comprise an alkyl having from 1 to 6 carbonatoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20carbon atoms, a nitro, or combinations thereof, or R⁴ and R⁵ can form asubstituted or unsubstituted cyclic ring having from 3 to about 12carbon atoms; wherein R⁶ and R⁷, independently, is optionallysubstituted and optionally contains heteroatoms; and is hydrogen; alinear or branched alkyl having from 1 to about 18 carbon atoms, an arylhaving from 6 to about 18 carbon atoms optionally saturated orunsaturated; an arylalkyl having from about 7 to about 18 carbon atoms;an alkenealkyl having from 3 to about 18 carbon atoms; or is derivedfrom a polyalkylene glycol ether having from 3 to about 200 carbonatoms; or is derived from piperazine, morpholine, pyrrolidone,piperidine, 4-alkyl amino-2,2,6,6-tetramethyl piperidine,1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine,phenothiazine, iminodibenzyl, phenoxazine,N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivativesthereof; or R⁶ and R⁷ can form a substituted or unsubstituted cyclicring having a total of from 4 to about 12 carbon atoms; and wherein saidsubstituents, independently, are the same as R¹³; R¹³ is optionallysubstituted, and is a linear or branched alkyl or alkylene having from 1to about 12 carbon atoms, an aryl optionally saturated or unsaturated;an arylalkyl having from about 7 to about 18 carbon atoms; an acyl; analkene group; an alkenealkyl having from 3 to about 18 carbon atoms; analkylene group; an alkoxyalkyl derived from a polyalkylene glycol orderived from a polyalkylene glycol monoalkyl ether having from about 3to about 200 carbon atoms or derived from a polyalkylene glycol monoarylether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;a phosphorous containing alkyl; or a substituted or unsubstituted arylring containing heteroatoms; wherein the R¹³ substituents comprise analkyl having from 1 to 6 carbon atoms; an aryl; a halogen such asfluorine or chlorine; a cyano group; an amino group; an alkene group; analkoxycarbonyl group; an aryloxycarbonyl group; a carboxy group; anacyloxy group; a carbamoyl group; an alkylcarbonyl group; analkylarylcarbonyl group; an arylcarbonyl group; an arylalkylcarbonylgroup; a phthalimido group; a maleimido group; a succinimido group;amidino group; guanidimo group; allyl group; epoxy group; alkoxy group;an alkali metal salt; a quaternary ammonium salt; a hydroxyl group; anether having a total of from 2 to about 20 carbon atoms; a nitro;sulfur; phosphorous; a carboalkoxy group; a heterocyclic groupcontaining one or more sulfur, oxygen or nitrogen atoms, or combinationsthereof; each R¹⁴ is derived from a polyol, wherein said polyolcomprises a hydrocarbon polyol and wherein R¹⁴ comprises an alkyl or analkylene group, or a substituted alkyl or alkylene group having from 2to about 200 carbon atoms, and wherein said substituted alkyl oralkylene group comprises oxygen, or a halogen; polyester polyol,polyether polyol, polyhydroxy polyester amide, hydroxyl-containingpolycaprolactone, hydroxyl-containing acrylic interpolymer,hydroxyl-containing epoxide, polyhydroxy polycarbonate, polyhydroxypolyacetal, polyhydroxy polythioether, polysiloxane polyol, ethoxylatedpolysiloxane polyol, polybutadiene polyol, hydrogenated polybutadienepolyol, polyacrylate polyol, halogenated polyester polyol, orhalogenated polyether polyol, or combinations thereof; wherein T is adivalent radical having a nitrogen atom directly attached to a carbonatom of a thiocarbonyl group, and wherein said m and said n,independently, is from about 1 to about 10,000; wherein said conjugateddiene monomer has a total of from 4 to about 12 carbon atoms; whereinsaid vinyl monomer has the formula

where R¹⁵ comprises hydrogen, halogen, C₁ to C₄ alkyl, or substitutedC₁-C₄ alkyl wherein the substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR¹⁷), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc, or an ammonium salt,acyloxy, aroyloxy(O₂CR¹⁷), alkoxy-carbonyl(CO₂R¹⁷), or aryloxy-carbonyl;wherein R¹⁶ comprises hydrogen, R¹⁷, CO₂H, CO₂R¹⁷, COR¹⁷, CN, CONH₂,CONHR¹⁷, O₂CR¹⁷, OR¹⁷, or halogen; R¹⁷, independently, comprises C₁-C₁₈alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl, heterocyclyl,aralkyl, or alkaryl, wherein the substituents independently comprise oneor more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts),sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato,cyano, silyl, halo and dialkylamino; or wherein said vinyl containingmonomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide,N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;styrene, α methyl styrene, C₁,-C₁₂ alkyl styrenes with substitute groupseither on the chain or on the ring, or combinations thereof; andreacting said thiocarbonate block copolymer with said polyurethaneblock.
 57. The process of claim 56, including neutralizing said blockcopolymer and forming a dispersion by adding said block copolymer towater; wherein said active hydrogen compound comprises a hydrocarbonpolyol having a total of from 1 to about 20 carbon atoms, a polyesterpolyol, a polyether polyol, polyhydroxy polyester amides,hydroxyl-containing polycaprolactone, hydroxyl-containing acrylicinterpolymer, hydroxyl-containing epoxide, polyhydroxy polycarbonate,polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol,ethoxylated polysiloxane polyol, polybutadiene polyol and hydrogenatedpolybutadiene polyol, polyacrylate polyol, halogenated polyester polyolor halogenated polyether polyol, or combinations thereof; including saiddispersant, wherein said dispersant comprises a side-chain containingalkylene oxide monomer wherein said alkylene oxide side chain units havefrom 2 to about 10 carbon atoms and are unsubstituted, substituted, orboth unsubstituted and substituted with at least about 50 wt. % of saidalkylene oxide groups being ethylene oxide; or wherein said dispersantmonomer has the formula (HO)_(x)Q(COOH)_(y), wherein Q is a straight orbranched hydrocarbon radical having 1 to 12 carbon atoms, and wherein xand y are 1 to 3; and wherein T is

wherein R⁸ and R⁹, independently, is optionally substituted and ishydrogen, a linear or branched alkyl having from 1 to about 18 carbonatoms, an aryl group having from about 6 to about 18 carbon atoms, anarylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl havingfrom 3 to about 18 carbon atoms, wherein the substituents can be thesame as described herein for R¹ and R²; wherein R¹⁰ is optionallysubstituted, or is non-existent, or an alkylene group having from 1 toabout 18 carbon atoms with about 1 to about 6 carbon atoms preferred, orderived from a polyalkylene glycol ether having from 3 to about 200carbon atoms, wherein the substituents can be the same as describedherein for R¹ and R² or are hereroatoms such as oxygen, nitrogen, sulfuror phosphorous; and wherein R¹¹ and R¹², independently, is an alkylenegroup having from 1 to 4 carbon atoms, with R¹¹ and R¹² having a totalof from about 3 to about 5 carbon atoms, wherein R¹¹ and R¹²,independently, is optionally substituted and wherein said substitutedare, independently, R¹ and R²; and wherein said isocyanate compoundcomprises an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate,or an aromatic polyisocyanate, or combinations thereof.
 58. The processaccording to claim 57, wherein said thiocarbonate is said Formula AA, orsaid Formula BB, or said Formula CC (mono), or said Formula CC (di), orsaid Formula EE (mono), or and said Formula EE (di), and reacting saidconjugated diene and said vinyl monomers into said thiocarbonate block;wherein said active hydrogen compound is said hydrocarbon polyol is adiol having from 2 to about 20 carbon atoms, or a polyester polyolderived from an organic polycarboxylic acid or an anhydride thereofhaving from 1 to about 20 carbon atoms and a diol having from 2 to about20 carbon atoms, or said polyether polyol having from 2 to about 15carbon atoms in the repeat group, or said polycarbonate derived from adiol and a diarylcarbonate, or combinations thereof; wherein said dienemonomer is 1,3-butadiene, isoprene, 1,3-pentadiene,2,3-dimethyl-1-3-butadiene, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene, or combinations thereof; and wherein saidvinyl monomer is methyl methacrylate, ethyl methacrylate, propylmethacrylate (all isomers), butyl methacrylate (all isomers),2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid,benzyl methacrylate, phenyl methacrylate, methacrylonitrile,alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate(all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate,isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate,acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethylmethacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutylmethacrylate (all isomers), N,N-dimethylaminoethyl methacrylate,N,N-diethylaminoethyl methacrylate, triethyleneglycol methacrylate;itaconic anhydride, itaconic acid; sodium and zinc salts; itaconic acidand 2-acrylamido-2-methyl-1-propanesulfonic acid; N-vinylimidazole,vinylpyridine N-oxide, 4-vinylpyridine carboxymethylbetaine, diallyldimethylammonium chloride, p-styrenesulfonic acid, p-styrenecarboxylicacid, 2-dimethylaminioethyl acrylate and its alkyl or hydrogen halidesalts, 2-dimethyl-aminoethyl methacrylate and its alkyl or hydrogenhalide salts, N-(3-dimethyl-aminopropyl)acrylamide,N-(3-dimethylaminoproyl)methacrylamide, diacetone acrylamide,2-(acetoacetoxy)ethyl methacrylate, 2-(acryloyloxy)ethyl acetoacetate,3-trialkoxysilylpropylmethacrylate (methoxy, ethoxy, isopropoxy),glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (allisomers), hydroxybutyl acrylate (all isomers), N,N-diethylaminoethylacrylate, triethyleneglycol acrylate, methacrylamide,N-methylacrylamide, N,N-dimethyl-acrylamide, N-tertbutylmethacrylamide,N—N-butylmethacrylamide, N-methylol-methacrylamide,N-ethylolmethacrylamide, N-tertbutylacrylamide, N—N-butyl-acrylamide,N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (allisomers), diethylaminostyrene (all isomers), alpha-methylvinyl benzoicacid (all isomers), diethylamino alpha-methylstyrene (all isomers),p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic sodium salt,trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate,tributoxysilylpropyl methacrylate, dimethoxy-methylsilylpropylmethacrylate, diethoxymethylsilylpropyl methacrylate,dibutoxy-methylsilylpropyl methacrylate, diisopropoxymethylsilylpropylmethacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropylmethacrylate, dibutoxy silylpropyl methacrylate, diisopropoxysilylpropylmethacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropylacrylate, tributoxysilylpropyl acrylate, dimethoxy-methylsilylpropylacrylate, diethoxymethylsilylpropyl acrylate, dibutoxy-methylsilylpropylacrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxy-silylpropylacrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate,diisopropoxysilylpropyl amiate, vinyl acetate, vinyl butyrate, vinylbenzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleicanhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone,N-vinylcarbazole, butadiene, isoprene, chloroprene, ethylene, andpropylene; wherein each said m and n is from about 5 to about 500;wherein, in each said formulation, each R¹ and R², independently, ismethyl, or phenyl; wherein each R³, independently, is an alkyl havingfrom 1 to about 18 carbon atoms; wherein each said R⁴ and R⁵,independently, is methyl or phenyl; wherein each said R⁶ and R⁷,independently, is a phenyl, an alkyl or a substituted alkyl having from1 to about 18 carbon atoms; wherein each said R¹³, independently, is analkyl or an alkylene having from 1 to about 6 carbon atoms; wherein saidaliphatic polyisocyanate has a total of from 5 to about 20 carbon atoms,wherein said cycloaliphatic polyisocyanate contains from about 6 toabout 20 carbon atoms, and wherein said aromatic polyisocyanate containsfrom about 8 to about 20 carbon atoms; and wherein said(HO)_(x)Q(COOH)_(y) dispersant comprises citric acid, dimethylolpropanoic acid (DMPA), dimethylol butanoic acid (DMBA), glycolic acid,thioglycolic acid, tartaric acid, dihydroxy tartaric acid, lactic acid,maleic acid, dihydroxymalic acid, or combinations thereof.
 59. Theprocess according to claim 58, wherein said conjugated diene monomer isbutadiene, isoprene, or combinations thereof; and wherein said vinylmonomer is C₁-C₁₈ acrylate; acrylic acid; C₁-C₈ monoalkyl and dialkylacrylamide; a combination of C₁-C₈ acrylate and methacrylate; acombination of said acrylamide and C₁-C₈ monoalkyl and dialkylmethacrylamide; wherein said R¹⁴ polyol is said substantiallyhydrocarbon polyol and wherein said alkyl or alkylene group, or saidsubstituted alkyl or alkylene group has from 2 to about 10 carbon atoms;wherein said aliphatic polyisocyanate comprises tetramethylenediisocyanate, hexamethylene-1,6-diisocyanate (HDI), decamethylenediisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylenediisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate,2-methyl-1,5-pentamethylene diisocyanate, or combinations thereof,wherein said cycloaliphatic polyisocyanate comprisescyclobutane-1,3-diisocyanate, 1,2-, 1,3- and 1,4-cyclohexanediisocyanates, 2,4- and 2,6-methylcyclohexane diisocyanate, 4,4′- and2,4′-dicyclohexyldiisocyanates, 1,3,5-cyclohexane triisocyanates,isocyanatomethylcyclohexane isocyanates, isocyanatoethylcyclohexaneisocyanates, bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4′- and2,4′-bis(isocyanatomethyl) dicyclohexane, isophorone diisocyanate,derivatives, dimers, or trimers thereof, or combinations thereof;wherein said aromatic polyisocyanate comprises 2,4- and2,6-hexahydrotoluenediisocyanate, 1,2, 1,3, and 1,4-phenylenediisocyanates, triphenyl methane-4,4′,4″-triisocyanate,naphthylene-1,5-diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI),2,4′-, 4,4′- and 2,2-biphenyl diisocyanates, 2,2′-, 2,4′- and4,4′-diphenylmethane diisocyanates (MDI), polyphenyl polymethylenepolyisocyanates (PMDI), mixtures of MDI and PMDI, mixtures of PMDI andTDI, aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylylenediisocyanates and m-tetramethylxylyene diisocyanate (TMXDI), or modifiedpolyisocyanates thereof including dimers and trimers, or combinationsthereof; wherein said dispersant is trimethylol propane monoethoxylatemethyl ether, DMPA, or DMBA, or combinations thereof; and wherein saidactive hydrogen compound is said hydrocarbon diol, said polyester diol,said polyether diol, or said polycarbonate diol.
 60. The processaccording to claim 56, wherein said block copolymer is an AB block or an(AB)_(n)A block copolymer where n equals 1 to about 20; and wherein saidA block is said thiocarbonate block and said B block is said urethaneblock.
 61. The process of claim 57, wherein said block copolymer is anAB block or an (AB)_(n)A block copolymer where n equals 1 to about 20;and wherein said A block is said thiocarbonate block and said B block issaid urethane block.
 62. The process of claim 59, wherein said blockcopolymer is an AB block or an (AB)_(n)A block copolymer where n equals1 to about 5; and wherein said A block is said thiocarbonate block andsaid B block is said urethane block.